JP6639898B2 - Transfer film - Google Patents

Description

  The present invention relates to a transfer film having a curable composition layer on a release substrate.

  Conventionally, a film provided with a thin functional layer to impart functions such as hard coat property and scratch resistance to plastic surfaces in a wide range of fields such as home appliance display boards, automobile parts, electric equipment covers, construction or furniture constituent materials, etc. Was pasted. On the other hand, in order to reduce the weight of the constituent materials and improve the recycling rate, by transferring only the functional layer once provided as a transfer film to the surface of the constituent material by in-mold molding, the scratch resistance of the constituent material products Techniques for improving chemical resistance and the like have been studied.

  A typical example of the functional layer is a scratch-resistant function which is a hard coat. Generally, in the case of a hard coat of a polyfunctional (meth) acrylic resin capable of obtaining high abrasion resistance, shrinkage upon curing by active energy rays is large, so that the film is largely deformed and the film is largely warped. Therefore, when the transfer layer is processed on the surface of the constituent material, the entire constituent material is largely warped due to the hard coat transferred from the transfer film to the surface of the constituent material when transferring the functional layer to the surface of the constituent material. This is a major challenge.

  In Patent Document 1, a transfer film provided with a hard coat layer having a thickness of 10 μm or more is obtained by applying a total of two times using a cured product of an ionizing radiation-curable resin containing a urethane (meth) acrylate oligomer. However, in this method, since the curing shrinkage is large, it is difficult to suppress the warpage generated in the transfer film and the component material after the transfer.

  In Patent Document 2, as a hard coat that can be used as a transfer foil (film), a high-hardness polyfunctional (meth) acrylate is blended with urethane acrylate to suppress curing shrinkage and improve low curl properties. I have. However, in this method, the curing shrinkage is reduced by mixing a large amount of urethane acrylate with low curing shrinkage in the polyfunctional (meth) acrylate used as the hard coat. However, in this method, since the hardness after photocuring is reduced by the urethane acrylate blend, it is necessary to compensate for the reduced hardness with an organosilica sol as an inorganic component.

  In the case of hard coats made of these (meth) acrylic resins, for example, post-processing such as heat treatment is required in order to eliminate warpage, and extra steps and processing costs are required in the production of a transfer film and the transfer processing to a material to be transferred. I'll get stuck.

JP-A-2007-118465 (released on May 17, 2007) JP 2010-107956 A (released May 13, 2010)

  SUMMARY OF THE INVENTION An object of the present invention is to provide a transfer film capable of imparting abrasion resistance and chemical resistance to the surface of a substrate to be transferred and having excellent characteristics with little warpage.

  The present inventors have conducted intensive studies to solve the conventional disadvantages described above, and as a result, a siloxane-based resin containing an epoxy structure excellent in scratch resistance, chemical resistance, and low warpage caused by low curing shrinkage, The present invention has been completed by using a transfer film provided as a hard coat layer on a resin sheet.

Hereinafter, the present invention will be described.
[1] A transfer film (TF1) having a cured layer of a thermosetting or photocurable resin composition (L2) on a support base material (L1) having a thickness of 1 μm to 1 mm having releasability. The resin composition is
The following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, A monovalent hydrocarbon group selected from an aryl group having from 25 to 25 and an aralkyl group having from 7 to 12 carbon atoms, and R ³ is each independently a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and a is 0 A silane compound (I) having a hydrolyzable silyl group, represented by the following formula:
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(In the formula, R ⁴ is selected from a substituted or unsubstituted alkyl group or alkenyl group having 1 to 10 carbon atoms and a substituted aryl group, and has no epoxy structure-containing group. R ² is each independently And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and R ³ is each independently Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2), and is a hydrolyzed / condensed product with a silane compound (II) having a hydrolyzable silyl group. A condensate (A) having a molar ratio of the silane compound (II) to the silane compound (I) of 0 or more and 9 or less, and a curing agent (B) for curing an epoxy group;
Regarding the condensate (A), the condensate (A) was directly bonded to the silicon atom of the condensate (A) with respect to the mole number X of the OR ³ group directly bonded to the silicon atom of the raw material silane compounds (I) and (II). A transfer film, wherein the ratio Y / X of the number of moles Y of ^three OR groups is 0 or more and 0.5 or less.
[2] The transfer film according to [1], wherein the curing agent (B) for curing the epoxy group is a cationic polymerization initiator.
[3] The transfer film according to [2], wherein the cationic polymerization initiator is a fluorinated phosphoric acid-based, antimonic fluoride-based, or fluorinated phenylboronic acid-based cationic polymerization initiator.
[4] The method for producing a transfer film according to any one of [1] to [3].
[5] The method for producing a transfer film according to [4], wherein the condensate (A) uses a neutral salt (C) as a hydrolysis / condensation catalyst.
[6] The neutral salt (C) used as a hydrolysis / condensation catalyst for the condensate (A) may be any one selected from the group consisting of a group 1 element ion and a group 2 element ion as a cation, and an anion The method of producing a transfer film according to [4] or [5], wherein the salt is a salt comprising a combination with any one selected from the group consisting of chloride ions, bromide ions, and iodide ions.

  According to the present invention, high scratch resistance is obtained by applying and curing a siloxane resin-based curable composition (L2) having an epoxy structure-containing group on a support material (L1) having releasability. It is possible to obtain a transfer film having low warpage characteristics due to low curing shrinkage. Further, a transfer product with a functional layer to which the functional layer is transferred can be obtained from the transfer film.

The curable composition (L2) comprising a siloxane-based resin having an epoxy structure-containing group according to the present invention comprises a silane compound having a hydrolyzable silyl group represented by the following general formulas (I) and (II). It contains a condensate (A) obtained by hydrolysis and condensation using a basic salt or a basic compound as a catalyst, and a curing agent (B) for curing an epoxy group.
General formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having from 25 to 25 and an aralkyl group having from 7 to 12 carbon atoms, and R ³ is each independently a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and a is 0 It is an integer of） 2.)
General formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(In the formula, R ⁴ is selected from a substituted or unsubstituted alkyl group or alkenyl group having 1 to 10 carbon atoms and a substituted aryl group, and has no epoxy structure-containing group. R ² is each independently And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and R ³ is each independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a is an integer of 0 to 2).

Further, the silane compound (II) is hydrolyzed and condensed using a basic compound or a neutral salt as a catalyst with a molar ratio of the silane compound (II) to the silane compound (I) of 9 or less, and has a weight average molecular weight of 30,000. or less, to the moles X of oR ³ groups bonded directly to silicon atoms silane compound (I) and the silane compound (II) has, moles of oR ³ groups bonded directly to silicon atoms condensate (a) has The ratio Y / X of the number Y is 0.5 or less.

<(A) Condensate>
The silane compound (I) having a hydrolyzable silyl group is represented by the following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having from 25 to 25 and an aralkyl group having from 7 to 12 carbon atoms, and R ³ is each independently a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and a is 0整数 2).

The silane compound (II) having a hydrolyzable silyl group is represented by the following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(In the formula, R ⁴ is selected from a substituted or unsubstituted alkyl group or alkenyl group having 1 to 10 carbon atoms and a substituted aryl group, and has no epoxy structure-containing group. R ² is each independently And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and R ³ is each independently A hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a is an integer of 0 to 2.)
It is represented by

Specific examples of the alkyl group in which the terminal at R ¹ of the general formula (I) is substituted with an epoxy structure-containing group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, Examples include an isoamyl group, a hexyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.

The epoxy structure-containing group in R ¹ of the general formula (I) only needs to contain an epoxy group, and examples thereof include an epoxy group, a glycidyl ether group, and an epoxycyclohexyl group.

R ^{2 in the} general formula (I) is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Such hydrocarbon groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, phenyl, tolyl, xylyl, naphthyl, Examples include a benzyl group and a phenethyl group.

R ^{3 in the} general formulas (I) and (II) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. From the viewpoint that the silane compound having a hydrolyzable silyl group is easily hydrolyzed and condensed, the alkyl group of R ³ preferably has 1 to 3 carbon atoms, and most preferably 1 carbon atom.

R ^{4 in the} general formula (II) is a group selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group and a substituted aryl group, and having no epoxy group.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, amyl, isoamyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and heptyl. , An isoheptyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and the like. Examples of the substituent of the alkyl group include a thiol group, an amino group, an isocyanate group, a (meth) acryloyl group, a phenyl group, and a chloro group. Examples of the alkenyl group include vinyl, allyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Group, cyclohexenyl group, bicyclohexenyl group, 6-heptenyl group, 7-octenyl group, decenyl group, pentadecenyl group, eicosenyl group, tricosenyl group, and the like. Examples of the substituted aryl group include a styryl group.

Among them, R ⁴ is an unsubstituted alkyl group, and has a carbon number of 3 or more and 10 or less from the viewpoint that storage stability is good, the curing rate is high, and cracking of the obtained coating film can be suppressed. And more preferably an alkyl group having 3 to 6 carbon atoms. When it is a substituted alkyl group, the alkyl group preferably has 3 or more and 10 or less, more preferably 3 or more and 6 or less, and the substituent is a phenyl group, a cyclohexyl group, or (meth) acryloyl. Groups are preferred. When it is an alkenyl group, a vinyl group or an allyl group is preferred. As the substituted aryl group, a styryl group is preferable. When the unsubstituted alkyl group has 2 or less carbon atoms, or when the substituted alkyl group is less bulky than a phenyl group, cyclohexyl group, or (meth) acryloyl group, a dense cross-linked structure is formed at the time of cross-linking, and gel is formed. May be changed. Further, when the alkyl group has 11 or more carbon atoms, or when the substituent is a bulkier than a phenyl group, a cyclohexyl group, or a (meth) acryloyl group in the substituted alkyl group, the hydrophobicity is increased and the hydrolysis rate is increased. In some cases, the temperature may be extremely reduced or the curing speed may be reduced.

  A in the general formulas (I) and (II) is an integer of 0 to 2, and is appropriately selected according to the physical properties required of the curable composition.

  Specific examples of the silane compound (I) include, for example, 1-glycidyloxymethyltrimethoxysilane, 1-glycidyloxymethylmethyldimethoxysilane, 1-glycidyloxymethyltriethoxysilane, 1-glycidyloxymethylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxy Propylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 4-glycidyloxybutyltrimethoxy Orchid, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 6-glycidyloxyhexyltrimethoxysilane, 6-glycidyloxyhexylmethyldimethoxysilane, 6- Glycidyloxyhexyltriethoxysilane, 6-glycidyloxyhexylmethyldiethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-glycidyloxyoctylmethyldimethoxysilane, 8-glycidyloxyoctyltriethoxysilane, 8-glycidyloxyoctylmethyl Diethoxysilane, 1- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 1- (3,4-epoxycyclohexyl) methylmethyl Dimethoxysilane, 1- (3,4-epoxycyclohexyl) methyltriethoxysilane, 1- (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3- (3 4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 3- (3,4-epoxycyclohexyl) Propylmethyl Ludiethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butylmethyldimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, 4 -(3,4-epoxycyclohexyl) butylmethyldiethoxysilane, 6- (3,4-epoxycyclohexyl) hexyltrimethoxysilane, 6- (3,4-epoxycyclohexyl) hexylmethyldimethoxysilane, 6- (3 4-epoxycyclohexyl) hexyltriethoxysilane, 6- (3,4-epoxycyclohexyl) hexylmethyldiethoxysilane, 8- (3,4-epoxycyclohexyl) octyltrimethoxysilane, 8- (3,4-epoxycyclohexyl) ) Okuchi Methyldimethoxysilane, 8- (3,4-epoxycyclohexyl) octyltriethoxysilane, 8- (3,4-epoxycyclohexyl) octylmethyldiethoxysilane, epoxytrimethoxysilane, epoxymethyldimethoxysilane, epoxytriethoxysilane, Epoxymethyldiethoxysilane, 1-epoxymethyltrimethoxysilane, 1-epoxymethylmethyldimethoxysilane, 1-epoxymethyltriethoxysilane, 1-epoxymethylmethyldiethoxysilane, 2-epoxyethyltrimethoxysilane, 2-epoxy Ethylmethyldimethoxysilane, 2-epoxyethyltriethoxysilane, 2-epoxyethylmethyldiethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxypropylmethyl Dimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxypropylmethyldiethoxysilane, 4-epoxybutyltrimethoxysilane, 4-epoxybutylmethyldimethoxysilane, 4-epoxybutyltriethoxysilane, 4-epoxybutylmethyldimethoxysilane Ethoxysilane, 6-epoxyhexyltrimethoxysilane, 6-epoxyhexylmethyldimethoxysilane, 6-epoxyhexyltriethoxysilane, 6-epoxyhexylmethyldiethoxysilane, 8-epoxyoctyltrimethoxysilane, 8-epoxyoctylmethyldimethoxysilane Examples thereof include silane, 8-epoxyoctyltriethoxysilane, and 8-epoxyoctylmethyldiethoxysilane.

As described above, from the viewpoint that the silane compound having a hydrolyzable silyl group is easily hydrolyzed and condensed, the alkyl group of R ³ in the general formula (I) preferably has 1 to 3 carbon atoms, and most preferably 1 carbon atom. It is. Further, from the viewpoint of the reactivity (mobility) of the epoxy group during curing, the number of carbon atoms of the alkylene group bonding the epoxy group and the silicon atom is important, and the number of carbon atoms is preferably 1 to 6, more preferably 2 or 3.

In consideration of the above viewpoints, as the silane compound (I), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropylmethyldimethoxysilane is preferred. Among them, compounds in which R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group and a 3-glycidyloxypropyl group are preferred.

Among the silane compounds (II), those in which R ⁴ in the general formula (II) is an unsubstituted alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and ethyltrimethoxysilane. Methoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, Butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, oxy Examples thereof include tyltrimethoxysilane, oxytylmethyldimethoxysilane, oxytyltriethoxysilane, and oxytylmethyldiethoxysilane.

Examples of the compound in which R ⁴ in the general formula (II) is a substituted alkyl group include the following. Here, the substituent is not particularly limited, but is preferably a thiol group, an isocyanate group, a (meth) acryloyl group, a phenyl group, a cyclohexyl group, or a chloro group from the viewpoint of availability.

  However, among these substituents, the thiol (mercapto) group may react with the epoxy group during the hydrolysis / condensation reaction of the hydrolyzable silyl group. It is preferable to select an epoxysilane compound having an epoxycyclohexyl group that is less susceptible to nuclear attack.

  On the other hand, a silane compound having an amino group or an acid anhydride group as a substituent is highly likely to react with an epoxy group during a hydrolysis / condensation reaction of a hydrolyzable silyl group over a mercapto group. It is not preferable to use it in the present application.

Examples of the compound in which R ⁴ is a thiol-substituted alkyl group include 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, and 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobuty Lutriethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 6-mercaptohexyltrimethoxysilane, 6-mercaptohexylmethyldimethoxysilane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexylmethyldiethoxysilane, 8-mercaptooctyl Examples include trimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltriethoxysilane, and 8-mercaptooctylmethyldiethoxysilane.

Examples of the compound in which R ⁴ is an isocyanate group-substituted alkyl group include 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 1-isocyanatomethyltriethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, 2-isocyanate Ethyltrimethoxysilane, 2-isocyanatoethylmethyldimethoxysilane, 2-isocyanatoethyltriethoxysilane, 2-isocyanatoethylmethyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyl Triethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 4-isocyanatobutyltrimethoxysilane, 4- Isocyanate butylmethyldimethoxysilane, 4-isocyanatebutyltriethoxysilane, 4-isocyanatebutylmethyldiethoxysilane, 6-isocyanatehexyltrimethoxysilane, 6-isocyanatehexylmethyldimethoxysilane, 6-isocyanatehexyltriethoxysilane, 6-isocyanate Hexylmethyldiethoxysilane, 8-isocyanatooctyltrimethoxysilane, 8-isocyanatooctylmethyldimethoxysilane, 8-isocyanatooctyltriethoxysilane, 8-isocyanatooctylmethyldiethoxysilane, and the like.

Examples of the compound in which R ⁴ is a (meth) acryloyl group-substituted alkyl group include 1- (meth) acryloyloxymethyltrimethoxysilane, 1- (meth) acryloyloxymethylmethyldimethoxysilane, and 1- (meth) acryloyloxymethyltrimethoxysilane. Ethoxysilane, 1- (meth) acryloyloxymethylmethyldiethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2- (meth) acryloyloxyethylmethyldimethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane Silane, 2- (meth) acryloyloxyethylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryl Loyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 4- (meth) acryloyloxybutylmethyldimethoxysilane, 4- (meth) acryloyl Oxybutyltriethoxysilane, 4- (meth) acryloyloxybutylmethyldiethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexylmethyldimethoxysilane, 6- (meth) acryloyloxy Hexyltriethoxysilane, 6- (meth) acryloyloxyhexylmethyldiethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 8- (meth) acryloyloxyoct Methyl dimethoxysilane, 8- (meth) acryloyloxy octyltriethoxysilane, 8- (meth) acryloyloxyoctyl diethoxysilane and the like.

Examples of the compound in which R ⁴ is a phenyl-substituted alkyl group include benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, and 3-phenylpropysilane. Rutriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, 6-phenylhexyltriethoxysilane Silane, and the like.

Compounds wherein R ⁴ is a cyclohexyl group-substituted alkyl group include cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, 2-cyclohexylethyltrimethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltrimethoxysilane, 3-cyclohexylpropyltriethoxysilane, 4-cyclohexylbutyltrimethoxysilane, 4-cyclohexylbutyltriethoxysilane, 5-cyclohexylpentyltrimethoxysilane, 5-cyclohexylpentyltriethoxysilane, 6-cyclohexylhexyltrimethoxysilane, 6- And cyclohexylhexyltriethoxysilane.

Examples of the compound in which R ⁴ is a chloro-substituted alkyl group include, for example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxy Silane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane and the like.

Examples of the compound in which R ⁴ is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, and allylmethyldimethoxysilane. Ethoxysilane, 1-oxetanyloxymethyltrimethoxysilane, 1-oxetanyloxymethylmethyldimethoxysilane, 1-oxetanyloxymethyltriethoxysilane, 1-oxetanyloxymethylmethyldiethoxysilane, 2-oxetanyloxyethyltrimethoxysilane, 2 -Oxetanyloxyethylmethyldimethoxysilane, 2-oxetanyloxyethyltriethoxysilane, 2-oxetanyloxyethylmethyldiethoxysilane, 3 -Oxetanyloxypropyltrimethoxysilane, 3-oxetanyloxypropylmethyldimethoxysilane, 3-oxetanyloxypropyltriethoxysilane, 3-oxetanyloxypropylmethyldiethoxysilane, 4-oxetanyloxybutyltrimethoxysilane, 4-oxetanyloxybutyl Methyldimethoxysilane, 4-oxetanyloxybutyltriethoxysilane, 4-oxetanyloxybutylmethyldiethoxysilane, 6-oxetanyloxyhexyltrimethoxysilane, 6-oxetanyloxyhexylmethyldimethoxysilane, 6-oxetanyloxyhexyltriethoxysilane, 6-oxetanyloxyhexylmethyldiethoxysilane, 8-oxetanyloxyoctyltrimethoxysilane, 8 Oxetanylmethyl oxy-octyl methyl dimethoxy silane, 8-oxetanyl oxy octyltriethoxysilane, 8-oxetanylmethyl oxy-octyl methyl diethoxy silane, and the like.
Examples of the compound in which R ⁴ is a substituted aryl group include p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like.

  In the condensate (A) of the present invention, each of the silane compounds (I) and (II) may be used alone or in combination of two or more.

  In the curable composition of the present invention, when scuff resistance and chemical resistance are required as physical properties of the cured product, it is important that crosslinking of the epoxy group in the condensate (A) proceeds sufficiently, and the silane compound The molar ratio of the silane compound (II) to (I) [= the number of moles of the silane compound (II) / the number of moles of the silane compound (I)] is from 0 to 9 by hydrolysis and condensation to form a condensate ( It is preferred to obtain A).

  Even if the molar ratio of the functional group other than the epoxy structure-containing group exceeds 9, a cured product having high scratch resistance and high chemical resistance can be obtained, but problems may occur in other properties such as curing shrinkage. . For example, when the molar ratio of the (meth) acryloyl group exceeds 9, a cured product having high scratch resistance and high chemical resistance can be obtained, but the curing shrinkage is larger than the crosslinking of the epoxy group. The warp of the resin sheet increases, and cracks may occur in the hard coat layer when an environmental load due to heat or humidity is applied.

  On the other hand, curing by the epoxy structure-containing group involves a ring-opening reaction, so that shrinkage is small, and a cured product can be obtained with almost no cure shrinkage.

  For example, when methyltrimethoxysilane is used as the silane compound (II), the organic group of the silane compound (I) has a low bulk and does not inhibit the curing of the epoxy group. The high siloxane ratio (the ratio of the sum of Si and O in the molecule) and the high siloxane crosslink density in the obtained condensate (A) combine to exhibit high scratch resistance and high chemical resistance. In consideration of the above viewpoint, the molar ratio is more preferably 0 or more and 7 or less, further preferably 0 or more and 6 or less, and particularly preferably 0 or more and 5 or less.

  The condensation degree of the condensate (A) of the present invention is preferably a 2- to 200-mer obtained by hydrolyzing and condensing a silane compound to form a siloxane bond, and more preferably a 4- to 100-mer.

  When the condensation degree of the condensate (A) is smaller than the tetramer, there is a concern that the condensate volatilizes at a high temperature or under a high vacuum. However, when the condensate (A) contains the silane compound (II), the average number of epoxy groups per molecule is preferably two or more.

  Further, when the degree of condensation of the condensate (A) is larger than 200 mer, there is a concern that the compatibility with an organic solvent, a cured product, or the like is significantly reduced.

  The weight average molecular weight of the condensate (A) of the present invention is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more. Further, the weight average molecular weight is preferably 30,000 or less, more preferably 28,000 or less, and still more preferably 25,000 or less.

  When the weight average molecular weight of the condensate (A) is less than 500 (and further less than 1,000), there is volatility, and part or all of the condensate (A) may volatilize before curing under high temperature or high reduced pressure. is there. If the weight average molecular weight exceeds 30,000, the compatibility with organic solvents, cured products and the like is reduced, and there is a possibility that the film may become cloudy when forming a coating film.

  The weight average molecular weight is a weight average molecular weight measured by GPC.

  Here, the weight average molecular weight of the siloxane resin can be controlled by appropriately selecting the amount of water used for the reaction and the type and amount of the catalyst. For example, the weight average molecular weight can be increased by increasing the amount of water initially charged.

The silicon atom contained in the condensate (A) relative to the mole number X of the OR ³ group directly bonded to the silicon atom contained in the silane compound (I) and the silane compound (II), which are the raw materials of the condensate (A) of the present invention, The ratio Y / X of the number of moles Y of the directly bonded OR ³ groups is preferably 0.5 or less, more preferably 0.3 or less, particularly preferably 0.2 or less, and substantially 0. Is most preferred.

  When Y / X exceeds 0.5, the coating film shrinks with the elapse of time after curing and cracks may occur, or the storage stability of the epoxy group may be impaired. In particular, when Y / X is 0.2 or less, there is almost no reaction with time after curing.

In addition, Y / X can be determined by measuring with ¹ H-NMR and ²⁹ Si-NMR.

  Here, Y / X can be reduced to 0.5 or less by appropriately selecting the amount of water and the type and amount of the catalyst. For example, the larger the amount of water, the more the hydrolysis is promoted, and the value of Y / X becomes lower.

  From the viewpoint of increasing the crosslinking density due to the epoxy groups in the cured product and improving the hardness and scratch resistance of the cured product, the residual ratio of the epoxy structure-containing group in the condensate (A), that is, the silane as the raw material The ratio of the number of moles of the epoxy structure-containing group in the condensate (A) to the number of moles of the epoxy structure-containing group in the compound (I) is preferably higher.

  Specifically, the residual ratio of the epoxy structure-containing group of the present invention is preferably at least 20%, more preferably at least 40%, even more preferably at least 60%.

The residual ratio of the epoxy structure-containing group can be determined by ¹ HNMR measurement.

Further, even when the residual ratio of the epoxy structural group in the condensate (A) and the number of epoxy structural groups in one molecule are small, when R ¹ , R ² and R ⁴ are not bulky groups, R ¹ , R ² , and R ⁴ are preferably non-bulky groups because the crosslink density resulting from the epoxy group in the cured product can be increased.

<Hydrolysis / condensation catalyst>
In synthesizing the condensate (A) of the present invention, the hydrolysis / condensation reaction is preferably performed using a neutral salt or a basic compound as a catalyst.

  By carrying out the hydrolysis / condensation reaction using a neutral salt or a basic compound as a catalyst, it becomes difficult to deactivate the epoxy group before and after the hydrolysis / condensation reaction and during storage.

  On the other hand, when the hydrolysis / condensation reaction is carried out using an acidic compound as a catalyst, the hydrolysis of the epoxy group is likely to occur simultaneously, and the residual ratio of the epoxy structural group decreases. Further, the obtained condensate (A) becomes acidic, and when the storage container is made of metal, it tends to cause rust, and when the storage container is made of resin, it tends to be deteriorated by hydrolysis. . On the other hand, the condensate (A) obtained by using a neutral salt or a basic compound as a catalyst has a low corrosive effect on a material used as a general-purpose storage container, and thus can be suitably used.

  Further, when the epoxy group is cured by cationic polymerization, it is not preferable that the remaining catalyst acts as a cation trapper, and from this viewpoint, it is sometimes preferable to use a neutral salt as a catalyst rather than a basic compound.

<(B) Curing agent for curing epoxy group>
The curing agent (B) for curing the epoxy group with respect to the epoxy group-containing siloxane condensate (A) of the present invention is not particularly limited, and any of those generally known as epoxy resin curing agents can be used. .

  Preferred curing agents include, for example, acid anhydride curing agents, cationic polymerization initiators, organic phosphorus compounds, amine curing agents, tertiary amines, and the like.

  When the curing agent (B) is a curing agent that promotes polymerization of an epoxy group in the condensate (A) (hereinafter, sometimes referred to as a “polymerization-type curing agent”), 0.5 to 10 parts by weight. Is preferable, and 0.5 to 5 parts by weight is more preferable.

  When the amount of the curing agent (polymerization type curing agent) that promotes the polymerization of the epoxy group is less than 0.5 parts by weight, the polymerization of the epoxy group may not proceed sufficiently. When the amount is more than 10 parts by weight, In some cases, due to an increase in the number of polymerization initiation points, the degree of polymerization of the epoxy group does not sufficiently advance. In some cases, it does not act as a polymerization initiation point and remains in the coating film as a plasticizer.

  When the curing agent (B) has active hydrogen and is a curing agent that undergoes an addition reaction with an epoxy group in the condensate (A) (hereinafter, may be referred to as an “addition type curing agent”). , 10 to 150 parts by weight, more preferably 30 to 150 parts by weight.

  When the amount of the curing agent (addition type curing agent) that undergoes an addition reaction with the epoxy group is less than 10 parts by weight, the curing may not proceed sufficiently. When the amount is more than 150 parts by weight, the curing agent is excessive. Although the crosslinking of the epoxy group proceeds sufficiently, the remaining curing agent (B) becomes a plasticizer, and the crosslinking density may not be sufficiently high.

  The details of the acid anhydride-based curing agent, the cationic polymerization initiator, the organic phosphorus compound, and other usable curing agents are described below.

(B-1) Acid anhydride curing agent From the viewpoint of heat resistance, an acid anhydride curing agent is preferable as the curing agent for curing the epoxy group in the present invention. The acid anhydride-based curing agent is classified into a polymerizable / addition-type composite curing agent.

  As the acid anhydride-based curing agent, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride , Polysebacic anhydride, poly (ethyloctadecanedioic anhydride), poly (phenylhexadecandioic anhydride), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride Acid anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bis trimellitate dianhydride, het Acid anhydride Nadic anhydride, methyl nadic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and the like.

  These acid anhydride curing agents may be used alone, or two or more kinds may be used in an optional combination and blending amount.

  When an acid anhydride-based curing agent is used, it is preferably used such that the equivalent ratio of the functional group in the curing agent to the epoxy group in the condensate (A) is in the range of 0.5 to 10. When the equivalent ratio is in the range of 0.5 to 110, unreacted epoxy groups and functional groups of the curing agent hardly remain, which is preferable.

(B-2) Cationic polymerization initiator As the curing agent for curing the epoxy group in the present invention, a cationic polymerization initiator is preferable from the viewpoint of physical properties such as abrasion resistance and chemical resistance of the obtained cured product. In addition, the cationic polymerization initiator is classified as a polymerization type curing agent.

  Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a cationic species and / or a Lewis acid by heat, and a photocationic polymerization initiator that generates a cationic species and / or a Lewis acid by light. In addition, there is no clear division between a thermal cationic polymerization initiator and a photocationic polymerization initiator, and some of them act as a curing agent against both heat and light.

  Examples of the thermal cationic polymerization initiator include onium salt-based cationic polymerization initiators such as sulfonium salts, ammonium salts, pyridinium salts phosphonium salts, and iodonium salts; combinations of aluminum complexes with silanol compounds, and combinations of aluminum complexes with bisphenol S And the like, or an aluminum complex composite-based cationic polymerization initiator such as fluorinated phosphoric acid-based, antimonic fluoride-based, and fluorinated phenylboronic acid-based cationic polymerization initiators.

  Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, and metallocene compounds.

  The cationic polymerization initiator can be obtained as a commercial product. For example, FC-520 [all manufactured by 3M Company], UVR-6990, UVR-6974 [all manufactured by Union Carbide], UVE-1014, UVE-1016 [all manufactured by General Electric], KI-85 [ Degussa, SP-15, SP-170 [Asahi Denka Co., Ltd.], SI-60L, SI-80L, SI-100L [Sanshin Kagaku Kogyo], CPI -100P, CPI-101A, CPI-200K, CPI-200S [manufactured by San-Apro Co., Ltd.], WPI-124, WPI-113, WPI-116, WPI-169, WPI-170, WPI-124 [manual, Wako Pure Chemical Industries, Ltd.], Road Sill 2074 [or more, made by Rhodia], IRGACURE PAG250, PAG290 [or more, B SF Co., Ltd.], and the like.

  Among these cationic polymerization initiators, onium salts are preferred from the viewpoint of handleability. Further, among the onium salts, diazonium salts, iodonium salts, sulfonium salts, and phosphonium salts are particularly preferable.

  These cationic polymerization initiators may be used alone, or two or more of them may be used in any combination and in any desired amount.

  The addition amount of the cationic polymerization initiator needs to be adjusted according to the generation amount and generation rate of the generated acid. However, the addition amount is 0.5 to 10 parts by weight based on 100 parts by weight of the condensate (A) (solid content). Preferably, it is 0.5 to 5 parts by weight, more preferably 0.1 to 5 parts by weight.

  It is preferable that the addition amount of the cationic polymerization initiator is in the range of 0.01 to 15 parts by mass because the abrasion resistance and chemical resistance of the cured epoxy resin are improved.

  Furthermore, when cured by cationic ring-opening polymerization using super strong acids such as fluorophosphates, fluoroantimonates, and fluoroborates, the polymerization of epoxy groups proceeds rapidly due to the high acid strength. Thus, a cured product having high abrasion resistance and chemical resistance can be obtained.

  Furthermore, a cured product obtained by using a cationic polymerization initiator as a curing agent (B) for curing an epoxy group specifically has a property of expanding when cured.

(B-3) Organic phosphorus compound As the curing agent for curing the epoxy group in the present invention, an organic phosphorus compound is preferable from the viewpoint of accelerating the effect reaction. In addition, the organic phosphorus compound is classified as a polymerization type curing agent.

  Examples of the organic phosphorus compound include organic phosphines such as tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine, and phenyl phosphine; methyl tributyl phosphonium dimethyl phosphate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl And phosphonium salts such as triphenyl borate and tetrabutyl phosphonium / tetrabutyl borate.

  These organic phosphorus compounds may be used alone, or two or more thereof may be used in any combination and in any desired amount.

  The addition amount of the organic phosphorus compound needs to be adjusted according to the generation amount and generation rate of the generated acid, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the condensate (A) (solid content). , 0.5 to 5 parts by weight.

(B-4) Amine-based curing agent As the curing agent for curing the epoxy group in the present invention, an amine-based curing agent (excluding a tertiary amine) is preferable from the viewpoint of availability and cost. In addition, the amine-based curing agent is classified as an addition-type curing agent.

  Examples of the amine-based curing agent (excluding the tertiary amine) include, for example, aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines.

  As aliphatic amines, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, Examples include bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetra (hydroxyethyl) ethylenediamine.

  Examples of the polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamine.

  Examples of the alicyclic amines include, for example, isophoronediamine, metacenediamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, and 3,9-bis (3 -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like.

  Examples of the aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 4,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl ) Ethylamine, diami Dimethyldiphenylmethane, α, α′-bis (4-aminophenyl) -p-diisopropylbenzene, and the like.

  These amine-based curing agents may be used alone, or two or more of them may be used in an optional combination and blending amount.

  The amine-based curing agent is preferably 10 to 150 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the condensate (A) (solid content).

(B-5) Tertiary amine As a curing agent for curing the epoxy group in the present invention, a tertiary amine is preferable from the viewpoint of availability and cost. Note that tertiary amines are classified as polymerization-type curing agents.

  Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. No.

  These tertiary amines may be used alone, or two or more of them may be used in any combination and mixing ratio.

  The tertiary amine is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the condensate (A) (solid content).

(B-6) Other curing agents As curing agents for curing the epoxy group in the present invention, acid anhydride-based curing agents, cationic polymerization initiators and organic phosphorus compounds, amine-based curing agents (excluding tertiary amines) ), Tertiary amines, for example, amide-based curing agents, phenol-based curing agents, imidazoles, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanates Curing agents, blocked isocyanate curing agents, and the like. These other curing agents may be used alone or in combination of two or more.

  When the condensate (A) of the present invention is cured by heat or light, if necessary, a (meth) acrylate compound (C), an epoxy compound (D), and metal oxide fine particles (E) may be mixed. Can be cured.

<(C) Neutral salt>
The neutral salt used in the present invention is a normal salt composed of a strong acid and a strong base.For example, as a cation, a group 1 element ion, a group 2 element ion, a tetraalkylammonium ion, a guanidium ion Any one selected from the group consisting of fluoride ions, chloride ions, bromide ions, group 17 element ions excluding iodide ions, sulfate ions, nitrate ions, and perchlorate ions as anions. It is a salt composed of a combination of heels.

  Specific compounds of the neutral salt in the present invention include, for example, lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, furanium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, chloride Radium, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, guanidium chloride; lithium bromide, sodium bromide, potassium bromide, rabidium bromide, Cesium bromide, francium bromide, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, radium bromide, tetramethylammonium bromide Tetraethylammonium bromide, Tetrapropylammonium bromide, Tetrabutylammonium bromide, Tetrapentylammonium bromide, Tetrahexylammonium bromide, Guanidium bromide; Lithium iodide, Sodium iodide, Potassium iodide, Ravidium iodide, Iodine Cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, iodide Tetrabutylammonium, tetrapentylammonium iodide, tetrahexylammonium iodide, guanidinium iodide; lithium sulfate, sodium sulfate, potassium sulfate, rabidium sulfate Cesium sulfate, furanium sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, tetramethylammonium sulfate, tetraethylammonium sulfate, tetrapropylammonium sulfate, tetrabutylammonium sulfate, tetrabutylammonium sulfate, tetrapentylammonium sulfate, tetrasulfate Hexyl ammonium, guanidinium sulfate; lithium nitrate, sodium nitrate, potassium nitrate, rabidium nitrate, cesium nitrate, francium nitrate, beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, radium nitrate, tetramethyl ammonium nitrate, tetraethyl ammonium nitrate, Tetrapropyl ammonium nitrate, tetrabutyl ammonium nitrate, tetrapentyl nitrate Ammonium, tetrahexyl ammonium nitrate, guanidium nitrate; lithium perchlorate, sodium perchlorate, potassium perchlorate, rabidium perchlorate, cesium perchlorate, francium perchlorate, beryllium perchlorate, magnesium perchlorate, Calcium perchlorate, strontium perchlorate, barium perchlorate, radium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrapropylammonium perchlorate, tetrabutylammonium perchlorate, perchloric acid Examples include tetrapentylammonium, tetrahexylammonium perchlorate, guanidium perchlorate, and the like. These neutral salts can be used alone or in combination of two or more.

  Among these neutral salts, from the viewpoint of use as a catalyst, as the anion, a highly nucleophilic group 17 element ion is more preferable, and as the cation, it is not bulky so as not to inhibit the nucleophilic action. When required, Group 1 element ions and Group 2 element ions are more preferable.

  Furthermore, considering availability and safety during handling, neutral salts include lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, and lithium bromide. Sodium, potassium bromide, rabidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, magnesium iodide, Calcium iodide and strontium iodide are particularly preferred.

  In the present invention, the larger the amount of the neutral salt used, the more the hydrolysis / condensation reaction of the silane compound is promoted.However, in consideration of the transparency of the condensate and the purification step, the smaller the amount, the better. .

  The amount of the neutral salt used in the present invention is preferably 0.000001 mol or more and 0.1 mol or less, more preferably 0.000001 mol or more and 0.01 mol or less, based on 1 mol of the hydrolyzable silyl group of the silane compound. It is particularly preferably from 0.000005 mol to 0.05 mol, and most preferably from 0.000005 mol to 0.01 mol.

<(D) Basic compound>
The basic compound used in the present invention is not particularly limited as long as it is basic, but, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, carbonate Inorganic bases such as potassium hydrogen and ammonia; and organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used.

  Among these, an inorganic base is preferable in consideration of the ease of removal from the condensate (A).

  In the present invention, the larger the amount of the basic compound used, the more the hydrolysis / condensation reaction of the silane compound is promoted.However, in consideration of the transparency of the condensate and the purification step, the smaller the amount, the better. .

  The amount of the basic compound used in the present invention is preferably 0.000001 mol or more and 0.1 mol or less, more preferably 0.000001 mol or more and 0.01 mol or less, based on 1 mol of the hydrolyzable silyl group of the silane compound. It is particularly preferably from 0.000005 mol to 0.05 mol, and most preferably from 0.000005 mol to 0.01 mol.

  When considered as a hydrolysis / condensation reaction catalyst for a silane compound containing an epoxy structural group, the residual ratio of the epoxy structural group after the hydrolysis / condensation reaction is high, and the corrosiveness of the condensate (A) to the storage container is lower. Also, from the viewpoint that the adverse effect on the human body is often low in the handling step, neutral salts are preferred.

In the manufacture of a condensate (A) of the present invention, the amount of water required for the hydrolysis and condensation reaction is 0.2 to 20 equivalents preferably against OR ³ group attached directly to the silicon atom, 0.4 3 equivalents are more preferred, and 0.45 to 2 equivalents are even more preferred.

If the amount of water is less than 0.2 equivalent, the curing shrinkage may be increased during hard coat curing due to the remaining OR ³ groups without being hydrolyzed. When the amount of water exceeds 20 equivalents, the rate of the hydrolysis / condensation reaction is too high, and a high-molecular-weight condensate is generated, which may lower the physical properties and transparency of the coating film.

  The production of the condensate (A) of the present invention is preferably carried out while refluxing a diluting solvent, alcohol generated by hydrolysis, etc., in consideration of production safety.

  The diluting solvent used in the production of the condensate (A) of the present invention refers to an alcohol or an ether compound, and is preferably water-soluble.

  The reason is that many of the silane compounds (I) and (II) used in the present invention have low compatibility with the neutral salt (A) and the water used for hydrolysis, so that the reaction proceeds smoothly. This is because the reaction solution is preferably compatible.

  On the other hand, ketone and ester solvents are not suitable because they have a carbonyl group and easily hinder the reaction.

  The boiling point of the diluting solvent used in the production of the condensate (A) of the present invention is preferably from 40 ° C to 250 ° C, more preferably from 50 ° C to 230 ° C, and particularly preferably from 60 ° C to 200 ° C.

  If the boiling point of the diluting solvent is lower than 40 ° C., it tends to be in a reflux state at a low temperature and hinder the reaction. If it is higher than 250 ° C., it is difficult to remove the solvent after the reaction if it is too high. In some cases, it is necessary to incorporate complicated steps.

  Specific examples of the diluting solvent used in the production of the condensate (A) of the present invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-methyl-2-propanol, 1-methoxy- Examples thereof include 2-propanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol dimethyl ether.

  These diluting solvents may be used alone or in combination of two or more.

  The amount of the diluting solvent used in the production of the condensate (A) of the present invention is preferably such that the total amount of the silane compounds (I) and (II) is 90% by mass or less as a total amount of water and the diluting solvent, and 30% by mass. % To 80% by mass, more preferably 40% to 80% by mass.

  If the amount of the diluting solvent used is too large, there is a concern that the concentration of the silane compound in the reaction system decreases and the reaction rate decreases. On the other hand, it is possible to improve the compatibility between water and the silane compound and to suppress the increase in viscosity in the system as the reaction progresses and to suppress the decrease in the reaction rate. It is.

  On the other hand, when one or both of the silane compounds (I) and (II) have high hydrophilicity, the progress of the condensation reaction after hydrolysis may be slowed down. This is because silanol groups generated by hydrolysis are dispersed and stabilized for reasons such as hydration, and contact and condensation reactions between silanol groups are less likely to occur. In such a case, the reaction may be promoted by adding a hydrophobic solvent.

  The reaction temperature in the production of the condensate (A) of the present invention is preferably in the range of 40 to 250 ° C, more preferably in the range of 50 to 230 ° C, and still more preferably in the range of 60 to 200 ° C.

  When the reaction temperature is lower than 40 ° C., the catalytic activity of the neutral salt tends to decrease, and the reaction time tends to greatly increase. When the reaction temperature is higher than 250 ° C., the organic substituent may cause a side reaction. There is a concern that it will be awakened and deactivated.

<(E) (meth) acrylate compound>
The (meth) acrylate compound (E) in the present invention is used for adjusting the adhesion to the substrate to be transferred, adjusting the transfer releasability, or the reaction heat at the time of curing when producing the transfer film of the present invention. Can be used for the purpose of adjusting the crosslinking density immediately after curing by light or heat.

  As the component (E), there is no particular problem as long as it is a compound having a (meth) acryloyl group used in ordinary radical curing.

  Specific examples of the (meth) acrylate compound (E) include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. Di (meth) acrylates such as tripropylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triisocyanuric acid tri (meth) acrylate A) tri (meth) acrylates such as acrylates; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; dipentaerythris Toruhekisa (meth) 4 or more functional (meth) acrylates such as acrylate.

  Furthermore, NK Oligo UA-122P, NK Oligo U-4HA, NK Oligo U-6LPA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AT-600, UA-306H, UA-510H (all manufactured by Kyoeisha Chemical) Polyfunctional urethane acrylates such as EBECRYL220, EBECRYL8210, and EBECRYL8311 (all manufactured by Daicel Cytec Co., Ltd.); NK oligo EA-1020, NK oligo EA-6310, and NK oligo EA-7120 (all, Multifunctional epoxy acrylates such as Shin-Nakamura Chemical Co., Ltd., Epoxy Ester 70PA and Epoxy Ester 3002A (both manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL 600 and EBECRYL 6040 (both manufactured by Daicel Cytec Co., Ltd.). be able to.

  The (meth) acrylate compound (E) may be used alone or in combination.

  The mixing ratio of the (meth) acrylate compound (E) to the condensate (A) in the curable composition of the present invention is preferably from 1 to 9900 parts by weight, preferably from 1 to 9900 parts by weight, based on 100 parts by weight of the condensate (A). 1900 parts by weight is more preferable, 1 to 900 parts by weight is more preferable, and 10 to 200 parts by weight is more preferable.

  If the mixing ratio of the component (E) to the condensate (A) is less than 1 part by weight, crosslinking by radical polymerization tends to fail to proceed sufficiently. If it exceeds 9900 parts by weight, crosslinking by the epoxy group cannot proceed sufficiently. Tend.

<(F) Epoxy compound>
The epoxy compound as the component (F) in the present invention can be co-crosslinked with the condensate (A) at the time of curing, and can be used for the purpose of lowering the viscosity of the condensate (A) and reducing the cost. .

  The epoxy compound (F) is not particularly limited as long as it has an epoxy group, and known compounds can be used, and examples thereof include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides. Examples of the aromatic epoxide include glycidyl ether of a monovalent or polyvalent phenol having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and a compound obtained by adding an alkylene oxide thereof). As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.) Is mentioned. Examples of the aliphatic epoxide include polyglycidyl ethers of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof (such as 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether) and aliphatic polybasic acids. Examples include polyglycidyl esters (such as diglycidyl tetrahydrophthalate) and epoxidized long-chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

  The mixing ratio of the epoxy compound (F) to the condensate (A) in the curable composition of the present invention is preferably 0 to 100 parts by weight, and more preferably 0 to 70 parts by weight based on 100 parts by weight of the condensate (A). Is more preferable, and 1 to 50 parts by weight is further preferable.

  When the mixing ratio of the epoxy compound (F) to the condensate (A) exceeds 100 parts by weight, the crosslinking by the epoxy group tends not to proceed sufficiently. This is because many epoxy compounds are bifunctional and many compounds such as a bisphenol structure are likely to have a planar structure. In the case of a polyfunctional epoxy compound, a condensate (A ) Due to reduced compatibility.

  When the transfer substrate of the transfer film is transparent, the condensate (A) and the (meth) acrylate compound (E) or the epoxy compound (F) must be compatible.

  If they are not compatible before curing, a cloudy cured product is obtained, and it is difficult to use as a transparent member. When the cured product is cloudy, the cured product of the condensate (A) and the component (E) or the component (F) is not bonded to each other, and an interpenetrating network (IPN) cannot be formed so much. And physical properties such as hardness, abrasion resistance, and chemical resistance tend to be slightly deteriorated.

  When it is compatible with each other and a transparent cured product is obtained, it is possible to form a dispersion / IPN on a nano scale and to exhibit high hardness, high scratch resistance, and high chemical resistance even if they are not bonded to each other. is there.

  On the other hand, when the cured product is not bonded to each other and is not three-dimensionally crosslinked and has a high molecular weight, the cured product may be transparent immediately after curing, but the IPN may be unraveled due to heat or humidity. In some cases, phase separation progresses and cloudiness may occur.

  From this viewpoint, it is preferable that the (meth) acrylate compound (E) and the epoxy compound (F) have low molecular weight. More specifically, the molecular weight of the (meth) acrylate compound (E) and the epoxy compound (F) in the present invention is preferably 30,000 or less, more preferably 25,000 or less, and preferably 20,000 or less. More preferred.

  The number of functional groups of the (meth) acrylate compound (E) and the epoxy compound (F) in the present invention is preferably 2 or more and less than 200, and more preferably 2 or more and less than 100.

  When the number of functional groups is less than 2, the cured product may not be three-dimensionally crosslinked and have a high molecular weight. Even if the cured product is transparent immediately after curing, it may become cloudy due to heat or humidity. When the number of functional groups is more than 200, the molecular weight of the (meth) acrylate compound (E) or the epoxy compound (F) becomes too large, and there is a concern that they will not be compatible before curing.

<(G) Metal oxide fine particles>
As the condensate (A) of the present invention, metal oxide fine particles (G) can be used, if necessary. By blending the metal oxide particles (G), the scratch resistance of the coating film may be further improved.

Examples of the metal oxide fine particles (G) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), zirconia (ZrO ₂ ), zinc oxide (ZnO), and titania (TiO ₂ ). , ITO (tin / indium oxide), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), and composite fine particles thereof.

  Among these, silica, alumina, zirconia and antimony oxide are preferred from the viewpoint of high hardness. In particular, silica fine particles and alumina fine particles are preferable in terms of availability, cost, surface hardness, and the like, and silica fine particles are particularly preferable.

  These metal oxide fine particles may be used alone or in combination of two or more.

  The metal oxide fine particles (G) in the present invention are preferably a powder or a solvent-dispersed sol.

  When the metal oxide fine particles are a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and δ-butyrolactone. And the like, esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. it can. Among them, alcohols, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate are preferred.

  The average particle diameter (average primary particle diameter) of the metal oxide fine particles (G) in the present invention is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 20 nm or less.

  When the average particle diameter of the metal oxide fine particles exceeds 100 nm, the transparency of the obtained coating film tends to be impaired.

  Commercially available silica fine particle dispersions include, as colloidal silica, methanol silica sol, IPA-ST, MGK-ST, NBA-ST, XBA-ST, DMAC-ST, MIBK-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. [all, manufactured by Nissan Chemical Industries, Ltd.], OSCAL series, ELECOM series [all, JGC Catalyst] Kasei Co., Ltd.].

  Further, as the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, etc. [manufactured by Nippon Aerosil Co., Ltd.], Sildex H31, H32, H51, H52, H121, H122, etc. [manufactured] , Asahi Glass Co., Ltd.], G220A, G220, etc. [The above are made by Nippon Silica Industry Co., Ltd.], SYLYSIA470 [Fuji Silysia Co., Ltd.], SG Flake [Nippon Sheet Glass Co., Ltd.], etc. Can be.

  Examples of the alumina fine particle dispersion include NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610 [all manufactured by BYK Japan KK], and examples of alumina isopropanol dispersion include AS-150I [Sumitomo Osaka Cement ( AS-150T (manufactured by Sumitomo Osaka Cement Co., Ltd.) as a toluene dispersion of alumina, and HXU-110JC (manufactured by Sumitomo Osaka Cement Co., Ltd.), alumina, titania as a toluene dispersion of zirconia Examples of powders and solvent dispersions of tin, tin oxide, indium oxide, zinc oxide and the like include Nanotech (trade name, manufactured by C-I Kasei Co., Ltd.).

  Among these, ELECOM V-8802 and ELECOM V-8804 (all manufactured by JGC Catalysts and Chemicals Co., Ltd.) have high dispersibility of fine particles in the coating solution, and the resulting coating film has high transparency, hardness, and abrasion resistance. It is preferable for further improvement.

  The amount of the metal oxide particles (G) to be used is preferably 0 to 100 parts by weight, more preferably 0 to 50 parts by weight, based on 100 parts by weight of the condensate (A).

  If the amount of the metal oxide particles (G) exceeds 100 parts by weight, a coating film may not be formed or the transparency of the coating film may decrease.

  In the present invention, since the metal oxide fine particles (G) do not adversely affect the strength of the coating film, there is no problem if they are present together with the condensate (A). However, some metal hydroxides, such as silanol groups on the surface of silica particles, have a high acidity and may cause cationic polymerization of an oxirane ring such as an epoxy group or vinyl ether. Concentration [the sum of the condensate (A) and the (meth) acrylate compound (E), the epoxy compound (F), and the metal oxide fine particles (G) divided by the total weight of the curable composition] is 0.1. It is necessary to adjust to ~ 0.6.

  If the concentration of the matrix in the curable composition is lower than 0.1, the viscosity of the coating liquid tends to be too low and the thickness of the coating film tends to be difficult to adjust. If the matrix concentration in the curable composition is higher than 0.6, gelation may occur during storage.

  When it is desired to increase the concentration, chemical modification for sealing silanol groups, such as alkoxylation of the surface of the metal hydroxide fine particles (G), is effective. The above-mentioned ELECOM V-8802, ELECOM V-8804, and the like are also products that have improved dispersion in organic components by sealing silanol groups, and are effective.

<(H) radical polymerization initiator>
In the present invention, when the (meth) acrylate compound (E) is used, or when the silane compound (II) used at the time of synthesizing the condensate (A) has a (meth) acryloyl group, radical polymerization is initiated as a curing agent. It is necessary to use agent (H).

  As the radical polymerization initiator (H), all compounds generally known as compounds that generate radicals by giving light or heat energy can be used.

  Those that can be used as radical species to be generated include carbon radicals, oxygen radicals, thiyl radicals, and the like, but compounds that generate thiyl radicals have poor storage stability, and it is difficult to inhibit polymerization using a general polymerization inhibitor. . From these viewpoints, a radical source that generates a carbon radical or an oxygen radical is preferable, and as the radical generator, for example, a photoradical generator, a thermal radical generator, or the like can be used. Hereinafter, specific examples thereof will be described.

(H-1) Photo-radical generator The photo-radical generator (h-1) in the present invention is a compound that generates a radical when exposed to an active energy ray, and acts as a polymerization initiator for the component (E). I do.

  Specific examples of the photoradical generator (h-1) include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, and benzyldimethylketal. , 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Carbonyl compounds, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Kill. IRGACURE series such as IRGACURE 184 and IRGACURE 819; DAROCUR 1173 and DAROCUR series such as DAROCUR TPO [all manufactured by BASF]; KAYACURE DETX-S; KAYACURE CTX etc .; And TAZ series such as TAZ-110 (all manufactured by Midori Kagaku Co., Ltd.) are commercially available.

  These photoradical generators (h-1) may be used alone, or a plurality of them may be used in combination in consideration of the curing speed and the like.

  The addition amount of the photo-radical generator (h-1) needs to be adjusted according to the amount of generated radicals and the target molecular weight. However, the amount is 0.05 to 100 parts by weight based on the (meth) acrylate compound (E). The amount is preferably 50 parts by weight, more preferably 0.1 to 30 parts by weight.

  When the added amount of the photo-radical initiator (h-1) is less than 0.05 part by weight, the generated radicals become insufficient, and the (meth) acrylate compound (E) may not be sufficiently cured, resulting in tackiness. When the amount is more than the weight part, problems such as coloring and deterioration of weather resistance tend to occur.

(H-2) Thermal radical generator The thermal radical generator (h-2) in the present invention is a compound that generates a radical by heating, and acts as a polymerization initiator for the component (E).

  Specific examples of the thermal radical generator (h-2) include typical polymerization initiators. Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, and lauroyl. Diacyl peroxides such as peroxide and acetyl peroxide; peroxy such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate Esters: percarbonates such as diisopropylperoxydicarbonate and di-sec-butylperoxydicarbonate; and azo compounds such as azobisisobutyronitrile.

  These thermal radical generators (h-2) may be used alone, or two or more may be used in combination in consideration of the curing speed and the like.

  The amount of the thermal radical generator (h-2) to be added needs to be adjusted according to the amount of generated radicals and the target molecular weight. However, the addition amount is 0.05 to 100 parts by weight of the (meth) acrylate compound (E). It is preferably 50 parts by weight, more preferably 0.1 to 30 parts by weight.

  When the addition amount of the thermal radical initiator (h-2) is less than 0.05 part by weight, the generated radicals become insufficient, and the (meth) acrylate compound (E) may not be sufficiently cured, and tack may be generated. When the amount is more than the weight part, problems such as coloring and deterioration of weather resistance tend to occur.

  Further, the photo radical generator (h-1) and the thermal radical generator (h-2) may be used as a mixture. When the photo radical generator (h-1) is used, a known polymerization accelerator such as a tertiary amine can be used in combination.

<Photosensitizer (I)>
In the curable composition of the present invention, when the cationic polymerization initiator (b-2) and the radical polymerization initiator (H) exhibit performance by irradiating active energy rays, their photosensitivity is reduced. For the purpose of improvement, if necessary, a photosensitizer (I) can be used.

  As the photosensitizer, a photosensitizer capable of absorbing light in a wavelength range that cannot be absorbed by the photoinitiator used is more efficient.

  The photosensitizer (I) is not particularly restricted but includes, for example, anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives and the like.

  Among them, those having a low oxidation potential and high excitation energy of singlet or triplet states involved in electron transfer are ideal, and from the viewpoint of photoinduced electron donating properties, anthracene derivatives, thioxanthone derivatives, and benzophenone Derivatives are preferred. More specifically, 9,10-dialkoxyanthracene, 2-alkylthioxanthone, 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p'-aminobenzophenone, 2-hydroxy-4- Alkoxybenzophenone, benzoin ether and the like can be mentioned. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, methyl 2-benzoylbenzoate, Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Loaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone , 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene and the like.

  These photosensitizers may be used alone or in combination of two or more.

  When the photosensitizer (I) is used, the addition amount may be appropriately adjusted depending on the desired curing speed, but is preferably 0.1 part by weight or more based on 100 parts by weight of the photoinitiator. 0.5 parts by weight or more is more preferable, 10 parts by weight or less is preferable, and 5 parts by weight or less is more preferable.

  If the amount of the photosensitizer (I) is less than 0.1 part by weight, the desired effect of the photosensitizer (I) tends to be hardly obtained. Or tend to lead to increased costs.

<Ultraviolet absorber (J)>
In the condensate (A) of the present invention, an ultraviolet absorber (J) can be used, if necessary. Examples of the ultraviolet absorber (J) contained in the condensate (A) include benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, and triazine-based ultraviolet absorbers for maintaining the transparency of the acrylic resin layer. .

  Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H. -Benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H- Benzotriazol-2-yl) phenol] and the like.

  Examples of the benzophenone-based ultraviolet absorber include, for example, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, 2,2-dihydroxy-4-methoxy Benzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be exemplified.

  Examples of the phenyl salicylate-based ultraviolet absorber include pt-butylphenylsalicylate.

  Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy- 4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5- Liazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- Examples thereof include 1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine.

  The content of the ultraviolet absorbent in the condensate (A) depends on the ultraviolet absorbing ability of the ultraviolet absorbent used and the thickness of the coating film obtained by curing the condensate (A). Preferably it is 0.01 to 3% by weight.

  When the content of the ultraviolet absorbent (J) is less than 0.01% by weight, the ultraviolet light resistance is insufficient, and when it exceeds 3% by weight, the condensate (A) is colored by the ultraviolet absorbent. And more than the saturated amount dissolved in the condensate (A), which tends to cause cloudiness. The ultraviolet absorber content in the condensate (A) is more preferably 0.02 to 2.5% by weight, particularly preferably 0.03 to 2.2% by weight, based on the condensate (A). is there.

<Curable composition (L2)>
The curable composition of the present invention necessarily contains the component (A) and further contains the components (B) to (J) as necessary. In order to adjust and impart other physical properties and functions, the curable composition further contains various components. May be appropriately compounded. For example, additives commonly used in coatings such as inorganic fillers, inorganic pigments / organic pigments, surfactants, plasticizers, dispersants, wetting agents, thickeners, and defoamers can be added.

  The curable composition of the present invention may contain a solvent.

  The solvent is not particularly limited, but ketones such as methyl isobutyl ketone and diisobutyl ketone; alcohols such as butanol and isopropyl alcohol; esters such as butyl acetate and isopropyl acetate; ethers such as diethylene glycol methyl ether and propylene glycol methyl ether. Are preferred from the viewpoint of availability. In particular, when the base material is a resin, it is preferable to use an ether-based or alcohol-based solvent in an amount of 30% by weight or more of the total solvent in order not to damage the base material.

  The amount of the solvent is preferably from 0 to 400 parts by weight, more preferably from 0 to 100 parts by weight, based on 100 parts by weight of the total of components (A) to (J).

  If the amount of the solvent is more than 400 parts by weight, the substrate may be damaged as described above, which is not preferable.

  The method for preparing the curable composition of the present invention is not particularly limited, and the above components are blended, if necessary, shielded from light, and mixed with a hand mixer or a static mixer, a planetary mixer, a disper, a roll, Conventional methods such as kneading at room temperature or under heat using a kneader or the like, dissolving and mixing the components using a small amount of a suitable solvent, and the like can be mentioned.

<Cured product>
The cured product of the present invention includes those obtained by curing the active energy ray-curable composition. The active energy rays to be irradiated at the time of curing include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and δ-rays. Ultraviolet rays are the most preferable in terms of cost and cost.

The irradiation amount of the active energy ray is preferably integrated quantity of light 50~10,000mJ / cm ^2, accumulated light quantity of 100~2,000mJ / cm ² is more preferable.

When the irradiation amount of the active energy ray is less than 50 mJ / cm ² , it takes a long time for curing due to a small amount of light, and the productivity may be deteriorated. On the other hand, when the irradiation amount of the active energy ray exceeds 10,000 mJ / cm ² , the curable composition may be decomposed and may not be cured cleanly.

  The cured product of the present invention includes those obtained by curing a thermosetting composition. At this time, the curing temperature is not particularly limited, and is usually preferably 300 ° C or lower, more preferably 200 ° C or lower, and still more preferably 150 ° C or lower. When curing at a temperature higher than 300 ° C., there is a concern that organic components in the condensate are decomposed.

<Preparation of transfer film (TF)>
A transfer film can be produced using the curable composition (L2) of the present invention.

  The transfer film (TF) of the present invention has a layer obtained by applying and curing a heat and photocurable resin composition (L2) on a support substrate (L1) having a thickness of 1 μm to 1 mm and having releasability. Transfer film.

  The transfer film of the present invention can be obtained by a production method including a step of applying the curable composition of the present invention to a substrate and a step of curing using an active energy ray or a heat source to form a cured film.

  The curable composition (L2) can be applied by, for example, dip coating, flow coating, spray coating, gravure coating, bar coating, spin coating, roll coating, flexographic printing, screen printing, and brushing. It can be performed by a coating method or the like.

  The thickness of the coating is suitably about 0.01 to 100 μm after curing.

  The curable composition (L2) of the present invention can provide a transfer film or a transfer product with a small warp even when the cured product has a thickness of 100 μm, but the cured product has a sufficiently high hardness and a low hardness. The range of 0.01 to 50 μm is more preferable as a region having no extra film thickness as a film having excellent warpage characteristics.

  When curing the curable composition, as described above, curing is performed by light irradiation by irradiation with active energy rays or a heat source.

  In the present invention, the support base material or the release base material (L1) constituting the transfer film is for supporting the curable resin composition (L2), and the type is particularly limited. Instead, all conventionally known films can be used.

  Specific examples of the support substrate (L1) include polyester films such as polyethylene terephthalate film, polyolefin films such as polyethylene and polypropylene, polycarbonate films, resin films such as acrylic resin films, triacetyl cellulose films, norbornene films, and cloths. , Paper and the like. Other than these, the support base material is not particularly limited, and for example, metals, ceramics, glass, cement, ceramic base materials, wood, paper, fibers, and the like can be suitably used.

  Among these, in the active energy ray irradiation curing, an organic resin base material is preferable from the viewpoint of taking advantage of the fact that high heat is not required at the time of curing, and in consideration of availability, heat resistance, cost, and handleability. Then, polyethylene terephthalate (hereinafter, referred to as “PET”) is preferable.

  Examples of the PET resin base material include PET ACE [manufactured by Sumitomo Bakelite Co., Ltd.], Estella, Estella Super [manufactured by Sekisui Molding Industry Co., Ltd.], PETERS [manufactured by Mitsubishi Plastics Corp.], PETEC [TAKIRON CORPORATION] )), Mineron [Mineron Kasei Kogyo Co., Ltd.], Polytec A-PET sheet [Polytec Co., Ltd.], A-PET resin sheet [Teijin Chemical Co., Ltd.], Tetoron [Teijin Co., Ltd.] And Lumirror (manufactured by Toray Industries, Inc.), Cosmo Shine (manufactured by Toyobo Co., Ltd.), and the like.

  In particular, from the viewpoint of taking advantage of the low curing shrinkage of the present invention and the productivity as a transfer film, a thin substrate that can be wound into a film by roll-to-roll processing is more preferable.

  The thickness of the support substrate having releasability in the present invention is preferably 1 μm to 1 mm, more preferably 1 μm to 300 μm, and still more preferably 1 μm to 200 μm.

  When the thickness of the supporting base material is less than 1 μm, the supporting base material may be broken due to stress applied during coating or a solvent contained in the coating liquid. On the other hand, when the thickness of the supporting base material is more than 1 mm, the rigidity of the base material itself increases, and the base material is hardly affected by stress such as curing shrinkage received from the coating applied to the surface, and has an advantage of low curing shrinkage. Can not be used. That is, even in the case of a cured product having a large curing shrinkage, warpage often does not occur.

  In the transfer film of the present invention, a support substrate having releasability is used as a substrate for providing the curable composition (L2). It is sufficient that the curable composition (L2) is transferred from the material, that is, the curable composition has a function of peeling off as a uniform film without destruction such as cracking. If the curable composition (L2) does not peel off from the selected support substrate during the production of the transfer film, a release layer may be separately provided on the support substrate.

  The composition for forming the release layer is not particularly limited, and conventionally known compositions such as silicone, olefin, acryl-melamine and the like can be used in order to impart a function of peeling the curable composition.

  In the transfer film of the present invention, in order to transfer the curable composition (L2) as a functional layer to the substrate to be transferred (K) and make it firmly adhered, if necessary, the transfer film may have a releasable property. A transfer film in which one or more layers called a primer layer or an adhesive layer are provided on the curable composition (L2) provided on a supporting substrate having the above.

  As a material constituting the primer or the adhesive layer, a known heat-sealing adhesive or pressure-sensitive adhesive can be used.

  Examples of the heat-sealable adhesive or pressure-sensitive adhesive include vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl chloride vinyl chloride resin, acrylic resin, butyral resin, epoxy resin, polyester resin, polyurethane resin, nylon resin, and acrylic adhesive. Agents, rubber-based adhesives, silicone-based adhesives, urethane-based adhesives, and the like. These may be used alone or in combination of two or more.

  The optimal thickness of the primer and the adhesive layer is in the range of 0.5 μm or more and 10 μm or less.

  The method for forming the primer layer or the adhesive layer constituting the transfer film of the present invention can employ an existing coating / printing method, for example, direct gravure, gravure reverse, microgravure, roll coat, curtain coat, die coat, Spray coat, Meyer coat, comma coat, screen printing, flexographic printing and the like can be mentioned.

  A conventionally known material is required as a material for forming a layer for providing a functional layer, which is a curable composition (L2), firmly on a transfer-receiving substrate (K) by heat or chemical action. Can be used according to Furthermore, as described in the section of the curable composition (L2), the components (B) to (J) and other physical properties and functions are adjusted and imparted to the materials constituting these layers as necessary. For this purpose, various known additives may be appropriately blended.

  For example, additives commonly used in coatings such as inorganic fillers, inorganic pigments / organic pigments, surfactants, plasticizers, dispersants, wetting agents, thickeners, and defoamers can be added.

  From the above, as the minimum constitutional example of the transfer film of the present invention, the support base material (L1) / curable composition (L2), the support base material (L1) / curable composition (L2) / adhesive layer, support Base material (L1) / curable composition (L2) / primer layer / adhesive layer, support base material (L1) / release layer / curable composition (L2), support base material (L1) / release layer / Curable composition (L2) / adhesive layer, support base material (L1) / release layer / curable composition (L2) / primer layer / adhesive layer. Further, a layer provided on the curable composition (L2) layer may be provided in addition to the above, if necessary.

  When it is desired to finally impart a pattern or the like to a transferred material using the transfer film of the present invention, in the structure of the transfer film (TF), (i) a PET film having releasability and a curable composition (L2) layer Or between (ii) the curable composition (L2) and the substrate to be transferred (K), or (iii) between the curable composition (L2) and the primer layer and the adhesive layer. A decorative layer may be provided as a layer. It is also possible to provide a decorative layer in advance on the layer to be transferred (K), and then transfer the transfer film of the present invention from above.

  The decorative layer has no particular difference in material as compared with the respective layers that can constitute the transfer film.

  The decoration techniques that can be employed in the formation of the decoration layer include not only general printing using color inks, but also special printing such as pearl, fluorescent light, mirrors, retroreflection, and magnetic printing; Conventionally known materials and methods can be used, such as an embossing process for forming an effect and a hologram, and a thin film forming technology for forming aluminum, silver, chromium, titanium oxide, zinc sulfide, or the like by vacuum evaporation or sputtering.

<Transfer material>
The transfer film according to the present invention is cured to the material to be transferred (K) by heating the outermost layer on the curable composition side of the transfer film while closely contacting the material to be transferred by using a method such as a hot roll press. It is possible to thermally transfer the functional layer formed by the conductive composition (L2).

  The transfer material (K) is not particularly limited in shape and the like, but as a preferable example, for example, an organic base material such as a resin sheet or a film or an inorganic base material such as a glass plate can be appropriately used. .

  In recent years, an organic base material is often used, and when used for a screen protection plate of a portable display terminal or the like, the organic base material is used as a material to be transferred in order to aim at a lightweight and hard-to-break characteristic. It is preferably a resin sheet or film.

  Specific examples of such a resin are not particularly limited as long as the resin is transparent at a visible light wavelength. For example, acrylic resin; PET; polycarbonate; polystyrene, styrene-acryl copolymer, acrylonitrile-butadiene-styrene copolymer (hereinafter, referred to as A plastic substrate such as a polystyrene resin such as “ABS”); a polyolefin resin such as polyethylene and polypropylene; a vinyl chloride resin; a thermosetting resin substrate; and the like are preferably used.

  The transfer material (J) preferably has a thickness of 0.1 mm or more and 50 mm or less.

  Further, as another method of transferring the transfer film to the material to be transferred (K), for example, in the case of an organic base material, as a step of producing the material to be transferred (J), the material to be transferred (K) is heated, Extrusion molding using a T-die or the like in a molten state, or when forming by a coating method such as a casting method in a state in which a material to be transferred (K) is dissolved in a solvent, By setting the layer (L2) having the curable composition as a support sheet, the molding of the material to be transferred and the transfer of the functional layer which is the curable composition can be performed by melting or cooling from a heated state or by a chemical action. It can be done at the same time.

  There are no particular restrictions on the method of transferring the functional layer contained in the transfer film to the material to be transferred (K), and a conventionally known method can be used.

  The transfer film of the present invention is obtained by transferring a hard coat layer or a functional layer such as chemical resistance to a substrate to be transferred, so that a front plate of a personal computer, a smartphone, a tablet or the like, a liquid crystal member, a window glass of an automobile or the like, an automobile or the like can be obtained. It can be suitably used for protective materials for lamps, building materials, home appliances and the like.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.

The substances used in the examples and comparative examples are as follows.
-Silane compounds having hydrolyzable silyl groups (I)
A-186: Momentive Performance Materials Japan GK, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, molecular weight 246.3
A-187: Momentive Performance Materials Japan GK, 3-glycidyloxypropyltrimethoxysilane, molecular weight 236.3
-Silane compounds having hydrolyzable silyl groups (II)
A-174: Momentive Performance Materials Japan GK, 3-methacryloxypropyltrimethoxysilane, molecular weight 248.4
A-1630: Momentive Performance Materials Japan GK, methyltrimethoxysilane, molecular weight 136.2
○ Neutral salt (C)
Magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade, molecular weight 95.2)
○ (meth) acrylate compound (E)
DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 578)
TMPTA: trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 296)
HDDA: Hexanediol diacrylate (Shin-Nakamura Chemical Co., Ltd., molecular weight 226)
-Curing agent (B) that cures epoxy groups
CPI-101A: manufactured by San-Apro Ltd., triarylsulfonium · SbF ₆ salt ALCH-TR: Kawaken Fine Chemicals Co., Ltd., aluminum tris ethylacetoacetate ○ radical generator (H)
2-hydroxy-2-methylpropiophenone: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 164.2

-Diluent solvent PGME: 1-methoxy-2-propanol (manufactured by Daicel Corporation, molecular weight 90)
Methanol (Mitsubishi Gas Chemical Co., Ltd., molecular weight 32)
○ Removable PET film PET film [Toyobo, 38 μm thick]
○ Adhesive layer laminated on the curable composition (L2) constituting the transfer film Thermoplastic polyamide resin [Henkel Japan K.K., Macromelt 6240] and polyvinyl butyral resin [Sekisui Chemical Co., Ltd.] , BX-1] at a solid content ratio of 1 / 0.2 was diluted with a mixed solvent of MEK / toluene / n-butanol = 1/1/1 to obtain a solution having a solid content of 20%. Material (K)
PET (polyethylene terephthalate) film [Lumirror, T-60, 38 μm thick, manufactured by Toray Industries, Inc.]
PMMA (polymethyl methacrylate) sheet [Deraglass, Asahi Kasei Corporation, 999, 2.0 mm thickness]
PC (polycarbonate) sheet [PC-1600, 2.0 mm thick, manufactured by Takiron Corporation]
ABS (acrylonitrile-butadiene-styrene copolymer) sheet (white) [manufactured by TP Giken Co., Ltd., ABS plate (white), 2.0 mm thick]
ABS sheet (black) [TP Giken Co., Ltd., ABS plate (black), 2.0 mm thick]
White PVC (polyvinyl chloride) sheet [KP45, 2.0 mm thick, manufactured by Sumitomo Bakelite Co., Ltd.].

  The evaluation of the condensate obtained in the synthesis example is as follows.

(Quantification of OR group directly bonded to silicon)
By the following method, the OR group directly bonded to silicon in the silane compound before and after the reaction was measured, and the Y / X ratio was calculated.

Using JNM-LA400 manufactured by JEOL Ltd., ¹ H-NMR and ²⁹ Si-NMR measurements were performed using heavy acetone as a solvent.

(Measurement of weight average molecular weight)
The weight average molecular weight was measured by GPC. That is, it was calculated in terms of polystyrene using HLC-8220GPC manufactured by Tosoh Corporation as a liquid sending system, TSK-GEL H type manufactured by Tosoh Corporation as a column, and THF as a solvent.

(Evaluation of residual epoxy group)
The obtained condensate was subjected to ¹ H-NMR measurement using JNM-LA400 manufactured by JEOL Ltd. with heavy acetone as a solvent.

  The evaluation of the physical properties of the transfer films and transfer products obtained in Examples and Comparative Examples is as follows. In addition, the evaluation with respect to a test piece was measured after hardening and leaving still at room temperature for 7 days.

(Scratch resistance)
Using an eraser abrasion tester [manufactured by Komoto Co., Ltd.], a load of 500 g / cm ² was applied to steel wool # 0000, and the resultant laminate was reciprocated 100 times on the coating surface to form a coating. I checked whether it got hurt.

(warp)
The transfer film obtained in the present invention, and a transfer product thereof are cut out in a square size of 100 mm × 100 mm, and the transfer film is horizontally oriented so that the surface on which the transfer film is transferred faces upward in the transfer film. It was left on a table.

  For each of the four vertices of the transfer film of the above size and the square of the transfer product, the distance in the vertical direction from the upper surface of the table was measured, and the average value was calculated. Positive values were obtained when the surface was warped on the painted surface side or the transfer surface (the lower surface was floating above the surface of the table), and negative values were obtained when the opposite was true.

  Further, in the transfer film, the curing shrinkage of the curable composition is large, and the warpage is large, so that the transfer film cannot maintain a square shape, that is, in a case where the transfer film is rounded into a cylindrical shape, the end face of the rounded cylindrical shape The diameter mm of a circle forming a round as viewed from above was measured, and “φ” was added before the measured value.

  It should be noted that the warpage of the PET film having the releasability to form the transfer film alone and the PC sheet as the transfer-receiving substrate were evaluated under the same conditions, and the result of the warpage was 0 mm.

<Synthesis Examples 1 to 7 of Condensate (A)>
The mixture shown in Table 1 (the unit of the blending amount is part by weight) was charged into a reactor equipped with a stirrer, a thermometer, and a reflux condenser, and stirred at the reaction temperature and reaction time shown in Table 1 to form a condensation product. I got something. The obtained condensate was devolatilized and concentrated under reduced pressure using an evaporator, and adjusted to a 50% solution using PGME.

  Table 1 shows the evaluation results for the obtained condensate.

<Example 1>
[Preparation of curable composition coating liquid (L2)]
Synthesis Example 1 as a condensate [A-186 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) condensate (50% solution)] 100 parts by weight of ALCH- as an epoxy group curing agent 1.5 parts by weight of TR was blended to prepare a coating solution. The coating liquid used was diluted with 27.3 parts by weight of PGME (1-methoxy-2-propanol) as a diluting solvent so that the nonvolatile content became 40%.

[Preparation of transfer film]
The obtained coating liquid was applied on a PET film (38 μm thickness) having releasability using a bar coater # 20 so that the dry film thickness became about 10 μm.
Next, the removal of the diluting solvent and the curing reaction were completed simultaneously (hereinafter, referred to as “thermal curing”) at 120 ° C. for 1 hour using a hot-air drier, followed by curing.
Further, in order to thermally transfer the cured curable composition (L2) and obtain good adhesion to the substrate to be transferred, an adhesive layer solution is applied onto the cured curable composition with a bar coater # 10. Was applied so that the dry film thickness was about 2 μm.

  Next, the solvent was removed at 120 ° C. for 3 minutes using a hot-air dryer, and the coating film was dried to prepare a transfer film.

[Preparation of transcript]
Using the obtained transfer film, in order to transfer to the polycarbonate (PC) sheet as the substrate to be transferred (K), the transfer film was set on the PC sheet so that the adhesive layer side of the transfer film was in contact with the roll, and a roll transfer device [ Navitas Co., Ltd., RH-300] at a roll temperature of 230 ° C. and a transfer speed of 50 mm / min, pressing the roll from the non-adhesive layer side of the transfer film to form the curable composition (L2). The layer and the adhesive layer were transferred to a PC sheet as a substrate to be transferred (K), and PET having releasability was peeled off to prepare a transfer product.

<Example 2>
A coating liquid was obtained in the same manner as in Example 1, except that the type and amount of the epoxy group curing agent were changed to WPI-124 / 1.0 parts by weight, and the amount of PGME was changed to 26.5 parts by weight. Then, after heating at 80 ° C. for 3 minutes using a hot air drier to remove the diluting solvent, the accumulated light amount at a wavelength of 310 to 390 nm and 1000 mJ / cm ^{2 at} 240 mW using a high-pressure mercury lamp in the air. The composition was cured by irradiating it with ultraviolet rays (hereinafter referred to as "ultraviolet curing"), and the same operation as in Example 1 was performed to obtain a transfer film and a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 3>
The same operation as in Example 2 was performed, except that the material to be transferred was changed to a polymethyl methacrylate (PMMA) sheet, to obtain a transfer film and further a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 4>
The same operation as in Example 2 was performed except that the transfer material was changed to an ABS sheet (white), to obtain a transfer film, and further a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 5>
The same operation as in Example 2 was performed, except that the transfer material was changed to an ABS sheet (black), to obtain a transfer film, and further a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 6>
The same operation as in Example 2 was performed, except that the transfer material was changed to a white polyvinyl chloride (PVC) sheet, to obtain a transfer film and further a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 7>
The same operation as in Example 2 was performed except that 53.57 parts by weight of V8804 (silica fine particles, 50% solid content) was added as the metal oxide fine particles, to thereby obtain a transfer film and further a transfer product.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 8>
The same operation as in Example 2 was carried out except that the condensate was changed to 100 parts by weight of Synthesis Example 2 [co-condensate of A186 and A1630 (methyltrimethoxysilane) (50% solution)], to thereby obtain a transfer film. And a transcript was obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 9>
A transfer film was obtained by performing the same operation as in Example 2 except that the condensate was changed to 100 parts by weight of Synthesis Example 3 [cocondensate of A186 and A1630 (50% solution)]. Obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 10>
The same operation as in Example 2 was carried out except that the condensate was changed to 100 parts by weight of Synthesis Example 4 [co-condensate of A186 and A174 (3-methacryloxypropyltrimethoxysilane) (50% solution)]. Then, a transfer film was obtained, and further a transfer product was obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 11>
The same operation as in Example 2 was carried out except that the condensate was changed to 100 parts by weight of Synthesis Example 5 [co-condensate of A186 and A174 (50% solution)] to obtain a transfer film. Obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 12>
The same operation as in Example 2 was carried out except that the condensate was changed to 100 parts by weight of Synthesis Example 6 [co-condensate of A186 and A174 (50% solution)] to obtain a transfer film. Obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Example 13>
The same operation as in Example 2 was carried out, except that the condensate was changed to 100 parts by weight of Synthesis Example 7 [co-condensate of A187 (3-glycidyloxypropyltrimethoxysilane) (50% solution)], the transfer was performed. A film was obtained, and a transcript was obtained.

  Table 2 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Comparative Example 1>
In [Preparation of curable composition coating liquid], a coating liquid was prepared in the same manner as in Example 2 using 100 parts by weight of DPHA, 3 parts by weight of 2-hydroxy-2-methylpropiophenone, and 154.5 parts by weight of PGME. I got Further, in [Preparation of transfer film], the same operation as in Example 2 was performed to obtain a transfer film and a transfer product.

  Table 3 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Comparative Example 2>
A transfer film and a transfer product were obtained in the same manner as in Comparative Example 1, except that the (meth) acrylate compound (E) was changed to TMPTA.

  Table 3 shows the physical property evaluation results for the obtained transfer film and transfer product.

<Comparative Example 3>
A coating liquid was obtained by the same operation except that the (meth) acrylate compound (E) was changed to HDDA, and a laminate was obtained by ultraviolet curing.

  Table 3 shows the physical property evaluation results for the obtained laminate.

<Comparative Example 4>
In [Production of curable composition coating liquid], 100 parts by weight of Synthesis Example 8 [co-condensate (50% solution) of A186 and A174 (3-methacryloxypropyltrimethoxysilane)], a curing agent for an epoxy group The same operation as in Example 2 was performed using 1.0 part by weight of WPI-124 and 25.8 parts by weight of PGME to obtain a transfer film and a transfer product.

  Table 3 shows the physical property evaluation results for the obtained transfer film and transfer product.

  In Examples 1 to 14, a transfer film comprising a cationically polymerized and cured epoxy group layer was obtained by using Synthesis Examples 1 to 7, and a transfer product using a transfer film was further obtained. The transfer product was small and had excellent scratch resistance, but hardly caused warpage of the laminate due to curing shrinkage.

  In Comparative Examples 1 to 4, a transfer film and a transfer product were obtained using a synthesis example in which the molar ratio of the silane compound (II) to the polyfunctional acrylate compound and the silane compound (I) was 9 or more, and highly crosslinked by an acryloyl group. Although the density is formed and the scratch resistance is excellent, the warpage is also increased due to the large curing shrinkage resulting from the high crosslinking density.

Therefore, the transfer film using each of Comparative Examples 1 to 4 is inferior in handleability after preparation and also has a large warp as a transfer product. For example, when used for a display panel of a portable information terminal that is an electronic device. In this case, there is a possibility that a problem that the quality of the product is deteriorated, such as floating of the display panel over time due to the warpage.
According to the present invention, for example, when used for a display panel of a portable information terminal that is an electronic device, since there is little warpage, the handleability is excellent, and there is less concern that the display panel floats due to the board warpage, and the quality is low. It is possible to provide stable products.

Claims (7)

A transfer film (TF1) having a cured layer of a thermosetting or photocurable resin composition (L2) on a support substrate (L1) having a releasability and having a thickness of 1 μm to 1 mm, wherein the curable resin composition is But,
The following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having from 25 to 25 and an aralkyl group having from 7 to 12 carbon atoms, and R ³ is each independently a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and a is 0 A silane compound (I) having a hydrolyzable silyl group, represented by the following formula:
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(In the formula, R ⁴ is selected from a substituted or unsubstituted alkyl group or alkenyl group having 1 to 10 carbon atoms and a substituted aryl group, and has no epoxy structure-containing group. R ² is each independently And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and R ³ is each independently Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2), and is a hydrolyzed / condensed product with a silane compound (II) having a hydrolyzable silyl group. A condensate (A) in which the molar ratio of the silane compound (II) to the silane compound (I) is 0 or more and 9 or less, a curing agent (B) for curing an epoxy group , and optionally, an epoxy compound (F ) And
Regarding the condensate (A), the condensate (A) was directly bonded to the silicon atom of the condensate (A) with respect to the mole number X of the OR ³ group directly bonded to the silicon atom of the raw material silane compounds (I) and (II). the ratio Y / X of moles Y of oR ³ groups Ri der 0 to 0.5,
A transfer film, wherein a mixing ratio of the epoxy compound (F) to the condensate (A) is 0 to 50 parts by weight based on 100 parts by weight of the condensate (A) . A transfer film (TF1) having a cured layer of a thermosetting or photocurable resin composition (L2) on a support substrate (L1) having a releasability and having a thickness of 1 μm to 1 mm, wherein the curable resin composition is But,
The following general formula (I):
_{^{R 1 - (SiR 2 a (}} OR 3) 3-a) (I)
(Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms whose terminal is substituted with an epoxy structure-containing group, and R ² is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. A monovalent hydrocarbon group selected from an aryl group having from 25 to 25 and an aralkyl group having from 7 to 12 carbon atoms, and R ³ is each independently a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and a is 0 A silane compound (I) having a hydrolyzable silyl group, represented by the following formula:
The following general formula (II):
_{^{R 4 - (SiR 2 a (}} OR 3) 3-a) (II)
(In the formula, R ⁴ is selected from a substituted or unsubstituted alkyl group or alkenyl group having 1 to 10 carbon atoms and a substituted aryl group, and has no epoxy structure-containing group. R ² is each independently And a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and R ³ is each independently Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2), and is a hydrolyzed / condensed product with a silane compound (II) having a hydrolyzable silyl group. A condensate (A) having a molar ratio of the silane compound (II) to the silane compound (I) of 0 or more and 9 or less, and a curing agent (B) for curing an epoxy group;
Regarding the condensate (A), the condensate (A) was directly bonded to the silicon atom of the condensate (A) with respect to the mole number X of the OR ³ group directly bonded to the silicon atom of the silane compounds (I) and (II) as the raw materials . The ratio Y / X of the number of moles Y of ^three OR groups is 0 or more and 0.5 or less;
A transfer film, wherein the curing agent (B) for curing the epoxy group is a cationic polymerization initiator .   The transfer film according to claim 1, wherein the curing agent (B) for curing the epoxy group is a cationic polymerization initiator. Transfer film according to the cationic polymerization initiator, fluorinated phosphate, antimony fluoride acid, characterized in that it is a cationic polymerization initiator fluoride phenylboronic acid, according to claim 2 or 3. It is a manufacturing method of the transfer film according to any one of claims 1 to 4 ,
Applying the curable composition to a support substrate (L1) having a releasability and having a thickness of 1 μm to 1 mm, and
A method for producing a transfer film, comprising a step of curing using an active energy ray or a heat source to form a cured film . The method for producing a transfer film according to claim 5 , wherein the condensate (A) uses a neutral salt (C) as a hydrolysis / condensation catalyst. The neutral salt (C) used as a catalyst for hydrolysis / condensation of the condensate (A) is any one selected from the group consisting of Group 1 element ions and Group 2 element ions as cations, and chloride as an anion ions, characterized in that bromide ion is a salt comprising a combination of any one selected from the group consisting of iodide ions, the manufacturing method of the transfer film according to claim 5 or 6.