JP6298678B2 - Coating composition for polycarbonate resin and coating product - Google Patents

Description

  The present invention relates to a coating composition for a polycarbonate resin and a coating product.

Polycarbonate resins are widely used from inexpensive general-purpose products to special products because they are lightweight and have excellent performance such as impact resistance, heat resistance, and flame retardancy.
Polycarbonate resin is also excellent in transparency, so optical applications and applications that require transparency, such as glasses, direction indicators for automobiles and motorcycles, various lenses such as taillights and headlights, electrical and electronic, optical It is used as a material for medical equipment, bulletproof glass, etc. Furthermore, it has been applied to lightweight windows for aircraft, automobiles, and bullet trains.

Polycarbonate resin is an engineering plastic that has overall excellent performance as described above, but on the other hand, sufficient characteristics are not obtained for weather resistance, solvent resistance, and scratch resistance. Have a problem.
With respect to solvent resistance and weather resistance, improvement is achieved by converting the polycarbonate resin into a polymer alloy.
In addition, the scratch resistance has been improved by performing a hard coat treatment on the polycarbonate resin, but the adhesion between the hard coat layer and the polycarbonate resin layer is not sufficient, and the flexibility is insufficient. Therefore, it is necessary to provide a primer layer. In such a case, it is also necessary to perform an edge treatment, which causes an increase in the number of steps and is disadvantageous in terms of cost.

Patent Document 1 proposes a composition containing polycarbonate diol, metal oxide colloidal particles, organosilane hydrolyzate, and a solvent as a material for a hard coating layer of a plastic lens made of a polycarbonate resin.
Patent Document 2 discloses an organic-inorganic hybrid polymer material effective for imparting scratch resistance, heat resistance, surface hardness, gas barrier properties, and water resistance while maintaining the transparency of the cured coating film. A technique obtained by using a modified polycarbonate diol and a metal alkoxide compound such as tetraethoxysilane has been proposed.
In Patent Document 3, an organic-inorganic hybrid polymer material effective for maintaining transparency, achieving both high adhesion and high hardness, and improving flex resistance is modified with polyethylene glycol. Techniques obtained with polycarbonate diol have been proposed.

  Patent Document 4 discloses a terminal-modified polycarbonate diol and a metal alkoxide compound that can be directly applied to an organic resin substrate without using an undercoat in order to express transparency and long-term adhesion, particularly at room temperature. A hard coat layer made of an organic-inorganic hybrid polymer material containing a solid material has been proposed.

JP 2006-251413 A JP-A-11-255883 Japanese Patent No. 3723891 JP 2011-037948 A

However, since the composition and the organic-inorganic hybrid polymer material disclosed in Patent Documents 1 to 3 both use tetrahydrofuran (THF) as a solvent, they are not suitable for use in a polycarbonate resin. In addition, there is a problem that sufficient adhesion cannot be obtained.
Further, the hard coat layer made of the organic-inorganic hybrid polymer material disclosed in Patent Document 4 has a problem that sufficient hardness cannot be obtained.

  Therefore, in the present invention, in view of the above-described problems of the prior art, a coating composition capable of forming a film on a polycarbonate resin, and capable of forming a coating film excellent in hardness, flexibility, and adhesion The purpose is to provide goods.

As a result of intensive studies to solve the above problems, the present inventors have found that a coating composition containing a polycarbonate diol, a predetermined alkoxysilane, and a polysiloxane oligomer can solve the above problems, and completed the present invention. It came to do.
That is, the present invention is as follows.

[1]
Polycarbonate diol,
Tetraalkoxysilane,
Trialkoxysilane,
A polysiloxane oligomer;
A coating composition for polycarbonate resin.
[2]
The coating composition for polycarbonate resin according to [1], wherein the polysiloxane oligomer includes an aromatic ring or an alicyclic cyclic compound.
[3]
The coating composition for polycarbonate resin according to [1] or [2], further including a metal complex.
[4]
The coating composition for polycarbonate resin according to any one of [1] to [3], wherein the polysiloxane oligomer has a weight average molecular weight of 300 to 1980.
[5]
The polysiloxane oligomer;
The mass ratio with the sum of the tetraalkoxysilane and trialkoxysilane is
The coating composition for polycarbonate resin according to any one of [1] to [4], wherein polysiloxane oligomer: (tetraalkoxysilane + trialkoxysilane) = 1: 10 to 1: 1.
[6]
Further comprising a medium,
The total mass of the tetraalkoxysilane, the trialkoxysilane, and the polysiloxane oligomer, and the mass ratio of the medium,
(Tetraalkoxysilane + trialkoxysilane + polysiloxane oligomer): Coating composition for polycarbonate resin according to any one of [1] to [5], wherein medium = 1: 2-30.
[7]
The coating composition for polycarbonate resin according to any one of [1] to [6], wherein the tetraalkoxysilane and / or the trialkoxysilane has a methoxy group.
[8]
The coating composition for a polycarbonate resin according to any one of [1] to [7], wherein the trialkoxysilane includes an aromatic ring or an alicyclic cyclic compound.
[9]
A coated product obtained by coating the polycarbonate resin coating composition according to any one of [1] to [8] on a polycarbonate resin substrate.
[10]
The coated product according to [9], which is heat-treated after the coating.

  ADVANTAGE OF THE INVENTION According to this invention, the coating composition for polycarbonate resins which can form the coating layer which has favorable adhesiveness to polycarbonate resin, is excellent in a softness | flexibility, and has sufficient hardness can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Coating composition for polycarbonate resin]
The polycarbonate resin coating composition of the present embodiment (hereinafter sometimes referred to as a coating composition) is:
Contains polycarbonate diol, tetraalkoxysilane, trialkoxysilane, and polysiloxane oligomer.

The coating composition of this embodiment is a coating composition for forming a coating film on a polycarbonate resin.
In the present specification, a polycarbonate resin, for example, a polycarbonate resin substrate formed with a coating film is referred to as a coating product.
The coating composition of this embodiment contains polycarbonate diol, tetraalkoxysilane, trialkoxysilane, and polysiloxane oligomer. Thereby, there exists an effect which adhesiveness with polycarbonate resin becomes a very favorable thing. In particular, as will be described later, by using an unmodified polycarbonate diol, the uniform dispersibility with the tetraalkoxysilane and trialkoxysilane is extremely good.

Each component of the coating composition of this embodiment is demonstrated in detail.
(Polycarbonate diol)
The coating composition of this embodiment contains a polycarbonate diol.
Polycarbonate diol is obtained by transesterifying diol and carbonate.

<Diol>
In the preparation of the polycarbonate diol, it is preferable to use a diol having a purity of 97% or more and 100% or less as a raw material diol. More preferably, it is 98% to 99.8%.

Examples of the raw material diol include, but are not limited to, for example, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, Diols having no side chain such as 1,7-heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol; 2 -Methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1 , 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, , 2-diol having a side chain of dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) - cyclic diol such as propane.
These may be used alone or in combination of two or more.
In addition, from the viewpoint of maintaining the strength of the fluidity of the obtained polycarbonate diol and the application using the polycarbonate diol, that is, the coating film, the intermediate with the coating film, the product with the coating, etc., two or more kinds of diols are used. Preferably used, a combination of 1,5-pentanediol and 1,6-hexanediol, a combination of 2-methyl-1,3-propanediol and 1,4-butanediol, 1,4-butanediol And 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol A combination with any one selected from the group is more preferred. Further, a combination of 2-methyl-1,3-propanediol, 1,4-butanediol and 1,5-pentanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol And a combination of 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol is more preferable.

Triols may be contained in the raw material diol.
Triols are preferably used in the range of 0.01 to 10% by mass, more preferably in the range of 0.05 to 5% by mass, based on the total amount of raw material diols used, that is, the preparation of polycarbonate diol and performance are not impaired. Is possible.
When the content of the triol is within the above range, gelation during the polymerization reaction of the polycarbonate diol can be prevented, and good transparency can be obtained.
The triols have three or more hydroxyl groups in one molecule and are not limited to the following, and examples include trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, and the like.

<Carbonate>
The carbonate as a raw material of the polycarbonate diol is not limited to the following. For example, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, tri Examples include methylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and alkylene carbonate such as 1,2-pentylene carbonate.
These carbonates may be used alone or in combination of two or more.
When dialkyl carbonate and / or diaryl carbonate is used as the carbonate, the target polycarbonate diol that can be used in the present invention can be easily obtained by adjusting conditions such as the charging ratio of the diol and the carbonate described above. Therefore, it is preferable.
Further, from the viewpoint of easy availability and ease of setting conditions for the polymerization reaction, it is more preferable to use ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or dibutyl carbonate as the starting carbonate.

Polycarbonate diol is obtained by transesterifying carbonate and diol. A conventionally known method can be used as a method for preparing the polycarbonate diol, and it is not limited to the following. For example, it is described in Schnell, Polymer Reviews Vol. 9, p9-20 (1994). It can be manufactured by various methods.
The reaction temperature for transesterification to obtain a polycarbonate diol is preferably 120 to 280 ° C, more preferably 140 to 230 ° C.
Although the molecular weight of polycarbonate diol is not specifically limited, 200-20000 are preferable from a stability viewpoint of the coating composition of this embodiment.
In addition, the polycarbonate may be derivatized such as terminal modification, or a derivative may be added. Furthermore, the polycarbonate diol may be a homo- or copolymer, but in the coating composition of this embodiment, from the viewpoint of uniform dispersibility with the tetraalkoxysilane and trialkoxysilane described later. It is preferable to use an unmodified polycarbonate diol, and it is more preferable to use a polycarbonate which is a copolymer from the viewpoint of flexibility.

In the preparation process of the polycarbonate diol, a catalyst may be added.
When adding a catalyst, a well-known transesterification catalyst can be used, and it is not specifically limited. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, tin, cobalt, germanium, lead, antimony, arsenic, cerium, titanium and other metals, alkoxides, their salts, organic Examples thereof include compounds, complexes thereof, complexes, and cross-coupling agents. In particular, from the viewpoint of the reaction time and the purity of the obtained polycarbonate diol, compounds of titanium, tin, lead and trans organic complexes are preferred.
Moreover, the usage-amount of a catalyst is 0.000005-0.5 mass% normally with respect to polycarbonate diol.

The content of the polycarbonate diol in the coating composition of the present embodiment is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and more preferably 5 to 20% with respect to the total amount of alkoxysilane. More preferably, it is 5 mass%, More preferably, it is 5-14 mass%.
By setting it as the said range, the coating composition of this embodiment is uniform and the outstanding softness | flexibility, followable | trackability, and transparency are obtained in a coating film.

(Polyfunctional alkoxysilane)
The coating composition of this embodiment contains tetraalkoxysilane and trialkoxysilane.
The coating composition of this embodiment may contain other polyfunctional alkoxysilanes other than tetraalkoxysilane and trialkoxysilane. Furthermore, a part of the alkoxysilane may be hydrolyzed.
By using polyfunctional alkoxysilanes including tetraalkoxysilane and trialkoxysilane, these can be hydrolyzed while including the polycarbonate diol described above, and further the condensation reaction can be advanced by heat treatment. Become. The hydrolysis condensate of alkoxysilane obtained by the reaction is included in the coating composition of this embodiment.

<Tetraalkoxysilane>
Examples of the tetraalkoxysilane include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetra-iso-propoxysilane, tetra-t-butoxysilane, and the like. Examples include silane tetrasubstituted with an alkoxy group having 1 to 4 carbon atoms. In particular, from the viewpoint of the uniformity of the coating composition and the maintenance of the reaction time and the hardness of the coating film, it preferably has a methoxy group, and more preferably tetramethoxysilane.

<Trialkoxysilane>
Examples of the trialkoxysilane include, but are not limited to, phenyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, ethyl Examples thereof include silane trisubstituted with an alkoxy group having 1 to 4 carbon atoms such as trimethoxysilane, vinyltrimethoxysilane, isopropyltrimethoxysilane, methyltri-iso-propoxysilane, and methyltri-t-butoxysilane.
Examples of those having an isocyanate group include 3-isocyanatepropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 2-isocyanatoethyltri-n-propoxysilane.
In particular, it is preferable to have a methoxy group from the viewpoint of the uniformity of the coating composition and the adhesion of the resulting coating film.
In the trialkoxysilane, examples of the remaining substituent include an alkyl group having 1 to 4 carbon atoms such as hydrogen, methyl, and ethyl, and an aromatic group such as a phenyl group, and an organic group such as methyl, ethyl, and phenyl. Groups are preferred. In particular, a phenyl group is more preferable because of high compatibility with all resins. Furthermore, phenyltrimethoxysilane is preferable from the viewpoint of the uniformity of the coating composition and the adhesion of the resulting coating film.

The trialkoxysilane preferably contains an aromatic or alicyclic cyclic compound.
Examples of aromatic cyclic compounds include, but are not limited to, phenyl (benzene), naphthalene, toluene, ethylbenzene, cumene, styrene, anthracene, triphenylene, tetraphen, pyrene, picene, pentaphen, and perylene. , Helicene, coronene, benzoanthracene, chrysene, benzofluoracene, benzopyrene, indenopyrene, dibenzoanthracene, phenanthrene, graphite, etc. , Tellurazole, morpholine, thiophene, pyran, pyridine, pyrimidine, pyrrolidine, piperidine, piperazine, indole, purine, quinoline, isoquinori , Quinuclidine, chromene, thianthrene, phenothiazine, furan, xanthene, acridine, furazane, phenazine, carbazole, selenazole, thiazole, oxazole, sydnone, and derivatives of these, and more like those of the alkyl substituents.
Examples of the alicyclic cyclic compound include, but are not limited to, for example, cycloalkanes, specifically, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, Cycloundecane, cyclododecane, cycloalkene for cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene, bicyclic alkane for bicycloundecane, decahydronaphthalene (decalin), bicyclic alkene for norbornene, Examples of norbornadiene and polycyclic compounds include cubane, basketane, houssan, spiro compounds, alicyclic epoxies, alicyclic amides, alicyclic acid anhydrides, alicyclic polyimides, and the like and their derivatives and derivatives.
When trialkoxysilane contains an aromatic or alicyclic cyclic compound, the compatibility of the coating composition, the adhesion to other resins, and the effect of improving followability can be obtained.
In particular, a phenyl group is more preferable because of high compatibility with all resins. Furthermore, phenyltrimethoxysilane is preferable from the viewpoint of the uniformity of the coating composition and the adhesion of the resulting coating film.

The content of tetraalkoxysilane in the total amount of silanes in the coating composition of the present embodiment is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, and 5 to 70% by mass. % Is more preferable. By setting it as the said range, the effect of the stability of a coating composition and the uniformity in a hardening process is acquired.
The content of trialkoxysilane in the total amount of silanes in the coating composition of the present embodiment is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, and 5 to 50% by mass. % Is more preferable. By setting it as the said range, the improvement effect of compatibility with an organic component is acquired.

(Polysiloxane oligomer)
The coating composition of this embodiment contains a polysiloxane oligomer.
The polysiloxane oligomer consists of products obtained by hydrolysis and condensation of various alkoxysilanes including tetraalkoxysilane and / or trialkoxysilane. Its structure is a complex mainly composed of T and D bodies.
In particular, the polysiloxane oligomer in the coating composition of the present embodiment is a composite of a product obtained by hydrolysis and condensation of tetraalkoxysilane, methyltrialkoxysilane, and phenyltrialkoxysilane. Is preferred. At this time, the ratio of the complex caused by methyltrialkoxysilane and the complex caused by phenyltrialkoxysilane is preferably 1 to 2 to 1.
The role of the polysiloxane oligomer in the coating composition of this embodiment will be described. When a coating film is formed using the coating composition, the entire polysiloxane oligomer or a part thereof is hydrolyzed and subjected to a heat condensation reaction with alkoxysilane which is another essential component. The reaction product thus obtained forms a network structure of a planar structure and a crystal structure with another essential component, polycarbonate diol. Thereby, more excellent appearance, adhesion to polycarbonate resin, flexibility, and coating film hardness can be obtained.

The polysiloxane oligomer used in the present embodiment may contain an aromatic ring or an alicyclic cyclic compound.
The content of the aromatic or alicyclic compound is preferably 10 to 45% by mass, more preferably 20 to 30% by mass, when the polysiloxane oligomer is 100% by mass. Thereby, the compatibility improvement with an organic substance and the improvement effect of the adhesiveness to various base materials are acquired.
Examples of aromatic cyclic compounds include, but are not limited to, phenyl (benzene), naphthalene, toluene, ethylbenzene, cumene, styrene, anthracene, triphenylene, tetraphen, pyrene, picene, pentaphen, and perylene. , Helicene, coronene, benzoanthracene, chrysene, benzofluoracene, benzopyrene, indenopyrene, dibenzoanthracene, phenanthrene, graphite, etc. , Tellurazole, morpholine, thiophene, pyran, pyridine, pyrimidine, pyrrolidine, piperidine, piperazine, indole, purine, quinoline, isoquinori , Quinuclidine, chromene, thianthrene, phenothiazine, furan, xanthene, acridine, furazane, phenazine, carbazole, selenazole, thiazole, oxazole, sydnone, and derivatives thereof. Moreover, these alkyl substituted bodies etc. are mentioned.
Examples of the alicyclic cyclic compound include, but are not limited to, for example, cycloalkanes, specifically, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclo Cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene, bicyclic alkanes for undecane, cyclododecane, and cycloalkenes; bicycloundecane, decahydronaphthalene (decalin) for bicyclic alkanes, norbornene, norbornadiene for bicyclic alkenes Polycyclic compounds include Cuban, Basketane, Hausan, Spiro compounds, cycloaliphatic epoxies, cycloaliphatic amides, cycloaliphatic anhydrides, cycloaliphatic polyimides and the like, and modified products and derivatives thereof, and cyclic silanes. It is done.

From the viewpoint of compatibility of the coating composition, the polysiloxane oligomer preferably has a weight average molecular weight of 200 to 3000, more preferably 300 to 1980, and still more preferably 1000 to 1980.
The weight average molecular weight of the polysiloxane oligomer can be measured by gel permeation chromatography (GPC).

The ratio of the polysiloxane oligomer and the sum of tetraalkoxysilane and trialkoxysilane is preferably (polysiloxane oligomer) to (tetraalkoxysilane + trialkoxysilane) = 1: 10 to 1: 1 by mass ratio. More preferably, it is 1: 5 to 1: 2, and still more preferably 1: 5 to 1: 3.
When the mass ratio is in the above numerical range, in the coating film formed using the coating composition of the present embodiment, high adhesion with the polycarbonate resin can be obtained, crack generation can be reduced, and high coating film hardness. Is obtained.
The ratio of tetraalkoxysilane and trialkoxysilane is not limited at all. From the viewpoints of reaction control and tact time, it is preferable to use a tetraalkoxysilane and then use a trialkoxysilane to control the reaction.

(catalyst)
In the coating composition of this embodiment, a predetermined catalyst is added for the purpose of improving the performance of the coating film formed using the coating composition or for the purpose of complementing the function of the polysiloxane oligomer described above. May be.
Examples of the catalyst include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, tin, cobalt, germanium, lead, antimony, and arsenic. , Metal alkoxides such as cerium and titanium, salts thereof, and organometallic alkoxides. Preferred are titanium, tin and lead compounds and phosphorus compounds, and more preferred are titanium and phosphorus compounds.
Moreover, 0.005-40 mass% is preferable with respect to the coating composition whole quantity (100 mass%) of this embodiment, and, as for the usage-amount of a catalyst, 0.05-30 mass% is more preferable.

(Medium)
The coating composition of this embodiment may further be mixed with a medium in addition to the above-described polycarbonate diol, alkoxysilanes, polysiloxane oligomer, and the above-described catalyst as necessary.
Examples of the medium include, but are not limited to, weak solvents such as water and alcohols, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, esters, and ethers. , Ketones, alicyclic hydrocarbons, aliphatic hydrocarbons, mixtures of aliphatic and aromatic hydrocarbons, glycols, glycol ethers, and the like.
These may be used alone or in combination of two or more.
The amount of the medium used is such that the ratio of the sum of the masses of the tetraalkoxysilane, trialkoxysilane, and polysiloxane oligomer and the mass of the medium is from the viewpoint of compatibility of the coating composition and reactivity of the coating composition ( Tetraalkoxysilane + trialkoxysilane + polysiloxane oligomer): (medium) = 1: 1 to 50, preferably 1: 2 to 30, more preferably 1: 5 to 20. preferable.
As the medium, use of glycol ethers is also preferable.
In the present embodiment, 1-methoxy-2-propanol is preferable as the medium for the purpose of preventing disproportionation and suppressing convergence during film formation.

Examples of the glycols and glycol ethers as the medium include, but are not limited to, ethylene glycol, propylene glycol, butyl glycol, 1,4-dioxane, 1,6-neopentyl glycol, and ethylene glycol. Monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether.
Among these, ethylene glycol monomethyl ether and propylene glycol monomethyl ether having a low boiling point are preferable.
As for the quantity of glycol and glycol ethers, 5-40 mol is preferable with respect to 1 mol of alkoxysilane mentioned above, More preferably, it is 10-30 mol.

(Metal complex)
The coating composition of this embodiment may further contain a metal complex.
Examples of the metal complex include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, tin, cobalt, germanium, lead, antimony, arsenic In addition, metal alkoxide having a core of cerium, titanium or the like, a salt thereof, aco (referring to H ₂ O), chlorine, sulfonic acid, sulfate radical, organic silane, or the like can be used as a ligand.
The content of the metal complex is preferably 0.5 to 30% by mass and more preferably 1.0 to 10% by mass in the coating composition.
By further including a metal complex in the coating composition of the present embodiment, the effect of maintaining the uniformity of the cured product can be obtained even when the curability is controlled, particularly when rapid curing is performed.

(Other alkoxysilanes)
The coating composition of this embodiment may contain (alkyl) alkoxysilane having an isocyanate group.
The (alkyl) alkoxysilane having an isocyanate group is not limited to the following, but examples of the trialkoxysilane include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoethyl. Tri-n-propoxysilane, and other compounds such as 3-isocyanatopropylmethyldimethoxysilane, 2-isocyanatoethyldibutoxysilane, 3-isocyanatopropyldimethylisopropoxysilane, 2-isocyanatoethyldiethylbutoxysilane, di (3-isocyanatopropyl) ) Diethoxysilane, di (3-isocyanatopropyl) methylethoxysilane, ethoxysilane triisocyanate and the like.

[Method for producing coating composition for polycarbonate resin]
The coating composition of this embodiment can be produced by the following method.
First, an acid (for example, nitric acid) and water are used as a catalyst, and a medium is added as necessary to obtain a mixed solution.
Alkoxysilanes composed of tetraalkoxysilane and trialkoxysilane are added to the mixed solution, and the mixture is stirred or statically cured to allow hydrolysis to some extent.
Thereafter, the coating composition is obtained by adding polycarbonate diol.
If necessary, a medium may be added to the polycarbonate diol. The medium in that case may be the same as or different from the medium added to the mixed solution.
The stirring is usually performed under a temperature condition of −20 ° C. to 180 ° C., but is preferably performed under a temperature condition of 35 to 80 ° C. from the viewpoint of handleability and the transparency of the coating film.

The amount of water as the acid (for example, nitric acid) catalyst or water as a catalyst contributing to equilibrium control affects the hydrolysis reaction and affects the performance of the coating film formed by the coating composition of the present embodiment. There are many (simultaneity of water catalytic effect and delay effect, acceleration by phase transfer, etc.).
From this viewpoint, the amount of water is preferably 2 to 6 mol, more preferably 3 to 5 mol, and still more preferably 3.5 to 4.5 mol, per 1 mol of alkoxysilanes.

The acid (for example, nitric acid) has a function of accelerating the hydrolysis reaction between polycarbonate diol and alkoxysilane, and is used for the stability of the coating composition of the present embodiment and the reproducibility of the physical properties of the coating film. It is preferable to do.
The acid as the catalyst is preferably about 0.001 to 0.10 mol per 1 mol of the alkoxysilanes described above. Furthermore, Preferably it is 0.002-0.05, Preferably, it is 0.005-0.02.
Examples of the acid include, but are not limited to, nitric acid, hydrochloric acid, sulfuric acid, acetic acid, various organic acids, and fruit acids. Nitric acid is particularly preferred from the viewpoint of controlling curability.
Use of an alkaline retarder in combination is also effective for controlling the performance of the coating composition of the present embodiment and the coating using the same.

  When preparing the coating composition of this embodiment, a thickener, an ultraviolet absorber, a light stabilizer, a heat ray absorber, colloidal particles of metal oxide, a curing catalyst, and a reaction catalyst are added as necessary. You may mix.

[Coating film using coating composition and coated product comprising the coating film]
A preferred example of a method for forming a film on a polycarbonate resin, for example, a polycarbonate resin substrate, using the coating composition of the present embodiment will be described below.
First, the coating composition of the present embodiment is applied to a polycarbonate resin under a temperature condition in the range of −20 ° C. to 180 ° C. by various commonly known coating methods.
Next, after drying at room temperature to 120 ° C. for 1 minute to 4 hours, if necessary, a cooling treatment is performed in a range of −20 to 10 ° C. as a cooling / heating set, or 60 ° C. to 150 ° C. as post-cure and annealing. Heat treatment is performed for 5 minutes to 12 hours at a temperature condition of ° C, or as a heat / cool repeated treatment, a cooling treatment of -20 ° C to 5 ° C and a heat treatment of 5 ° C to 180 ° C are repeated 1 to 20 times. You may go.
Thereby, the coating film which comprises a coating film and the said coating film is obtained.

[Use]
The coating composition for polycarbonate resin according to the present embodiment can form a coating film having good adhesion to the polycarbonate resin, coating film hardness, flexibility, and surface hardness, which has been a problem of the polycarbonate resin in the past. By combining flexibility, it can be used for many purposes. In particular, it is effective as a coating composition for polycarbonate resin that forms a hard coat layer for resin glass for automobiles and plastic lenses.

Hereinafter, the present invention will be described in detail with specific examples and comparative examples, but the present invention is not limited to the following examples.
The physical property values in the following examples and comparative examples were measured by the following methods.

[Method for evaluating physical properties]
(Appearance evaluation)
<Hydrosol solution>
The coating composition produced by the Example and comparative example which are mentioned later was extract | collected to the 10cc test tube, and the uniform (transparence, turbidity) condition was visually determined under the white fluorescent lamp.
A clear black paper placed 5 cm ahead of the test tube without any turbidity was judged as “transparent and uniform”.
<Coating film>
The coating composition manufactured by the Example and comparative example which will be described later is applied to 2 mm-thick polycarbonate resin, manufactured by Teijin Kasei Co., Ltd., Panlite PC-1511 with a bar coater of No. 300 or less, at 120 ° C. to 150 ° C. The coating obtained by heat-curing for 2 hours or 12 hours was observed visually and 40 times as large as a microscope, and only 2 mm thick polycarbonate resin, manufactured by Teijin Chemicals Ltd., Panlite PC-1511 was used. Compared with the resin plate obtained by heating under the conditions, those that were transparent in any evaluation were judged as “uniformly transparent”.
A lacquer blackboard placed on the tip of the coating film was cloudy, or a transmittance meter: UV-visible spectrophotometer (V-530 manufactured by JASCO Corporation), transmittance 80 Those that were less than% were judged as “domains”.

(Film thickness)
The film thickness of the coating film formed with the coating composition manufactured by the Example and comparative example which are mentioned later was measured.
The coating composition manufactured by the Example and comparative example which are mentioned later on the polycarbonate resin substrate (Asahi Glass Co., Ltd. Lexan 8010) with a thickness of 0.12 mm was applied with a bar coater of No. 300 or less, and at 120 to 150 ° C. A test piece was obtained by heat treatment for 2 hours or 12 hours, and the thickness of the coating film of the test piece was measured.
For film thickness measurement, a film thickness measuring instrument (Seiko EM Co., Ltd., Tetsutaro Co., Ltd.) was used to measure 10 randomly determined film thicknesses per sample, and the arithmetic average value was taken as the sample film thickness. .

(Surface observation Coating film cracks)
The coating composition manufactured by the Example and comparative example which are mentioned later on a 2 mm-thick polycarbonate resin substrate (manufactured by Teijin Kasei Co., Ltd., Panlite PC-1511) was applied with a bar coater of No. 300 or less, and 120 ° C. to 150 ° C. Test pieces are obtained by heat treatment at ℃ for 2 hours or 12 hours, and macro cracks such as hair cracks are observed at a magnification of 40 times with a microscope, and fine micro cracks are observed at (object) 480 times. Then, the presence or absence of cracks was determined, and no crack was defined as no crack at any magnification.

(Pencil scratch test: pencil hardness)
Based on JIS K5400, a pencil scratch test for coating film was performed.
2 mm thick polycarbonate resin substrate (Teijin Kasei Co., Ltd., Panlite PC-1511, Takiron Co., Ltd., PC-1600, referred to as PC board in Table 1), soft glass board (made by Kojima Special Glass Co., Ltd. Each of these was coated with a coating composition produced in Examples and Comparative Examples described below using a bar coater of No. 300 or less, and the coating composition was 120 ° C. to 150 ° C. for 2 hours or 12 hours. A heat treatment was performed to obtain a test piece having a coating film.
In the pencil scratch test, the test piece was attached to a test stand and moved horizontally to perform a scratching operation with a pencil placed on the test piece, and the hardness was determined by the scratches at that time.
The determination of the presence or absence of the scratch was performed from 45 ° obliquely with the coating film surface at 0 °.
The maximum hardness of a pencil without scratches (using a density symbol) was expressed as pencil hardness.

(Bending test: Bending resistance)
The bending test is a test performed to confirm the resistance of the coating film from peeling off from the coating, and was performed by the cylindrical mandrel method described in JIS K-5600-5-1.
Thereby, the resistance to peeling of the coating film was evaluated.
First, the coating composition manufactured by the Example and comparative example which are mentioned later was applied to the polycarbonate resin substrate (Asahi Glass Co., Ltd. Lexan 8010) with a thickness of 0.12 mm with a bar coater of No. 300 or less, and 120 ° C. to 150 ° C. A test piece having a coating film was obtained by heating at 12 ° C. for 2 hours or 12 hours.
Next, bending at 180 ° C. was performed along a round bar having a predetermined diameter, and the occurrence of cracks in the coating film was examined. The diameter of the round bar when cracking occurred was defined as the bending resistant diameter (mm).

  Furthermore, as a confirmation of the above uniformity and the presence or absence of cracks, in Example 13, the coating film applied to the glass substrate was heated at 600 ° C. or higher, and the organic matter was baked and removed, followed by the nitrogen adsorption method (Langmuir bed adsorption method). The coating film pores were confirmed, but it was in the range without any problems, and from the adsorption characteristics, uniform and short-period dispersion, that is, no organic matter was uniformly dispersed without cracks was confirmed. .

(Adhesion evaluation (cross-cut peel test))
A cross-cut peel test was performed in accordance with JIS K5400.
The coating compositions produced in Examples and Comparative Examples described later on a 2 mm thick polycarbonate resin substrate (Teijin Chemicals, Panlite PC-1511, Takiron, PC-1600) were applied with a bar coater of No. 300 or less. Coating was performed, and heat treatment was performed at 120 ° C. to 150 ° C. for 2 hours or 12 hours to obtain a test piece.
Vertically at intervals of 5 mm on the surface of the coating film of the test piece using a blade specified in JIS, a blade thickness width of 0.38 mm, and a cutting edge angle of 22 ° ± 2 ° (NT cutter eA-300). Eleven score lines were formed.
Next, the direction was changed by 90 °, 11 cut lines were formed on the side, and a grid-like cut line was formed as a whole.
Next, an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd., adhesive strength of 2.94 N / 10 mm or more) is applied to the width of 50 mm on the grid-like cut line, and the tape is applied with an eraser or the like (no particular regulation). The adhesive tape was peeled off 2 minutes after the adhesive tape was applied, and the adhesion state of the coating film to the adhesive tape was visually observed.
The evaluation criteria are shown below.
10: Each cut is thin and smooth on both sides, and there is no peeling between the intersection of the cut and the square.
8: There is a slight peeling at the intersection of the cuts, there is no peeling at a glance of the square, and the area of the defect is within 5% of the total square area.
6: There are peeling on both sides of the cut and the intersection, and the area of the missing part is 5 to 15% of the total square area.
4: The width of the peeling due to the cut is wide, and the area of the missing part is 15 to 35% of the total square area.
2: The width of the peeling due to the cut was wider than 4 points, and the area of the defect portion was 35 to 65% of the total square area.
0: The area of peeling is 65% or more of the total square area.

(Solvent resistance test (swelling of film, adhesion))
Further, as a confirmation of adhesion, the solvent resistance of the coating film is determined by using a solvent used in Examples described later: 1-methoxy-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Including those used as membrane aids), specifically 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 1,6-hexanediol, glycerin, ethylene glycol monobutyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran, acetone, methanol, ethanol (all manufactured by Tokyo Chemical Industry) Target Check the state of swelling of the coating film and adhesion to the base material immediately after dropping a predetermined solvent, called a love test and drop test, and then wear Qualatec gloves (made by full embossing, powder-free ASONE) It verified by carrying out the test which rubs with an index finger.
In Examples 1-14, there was no change of a coating film, such as swelling and peeling, and there was no problem. In particular, for Examples 3, 12, and 13, 1-methoxy-2-propanol used in the system shown in the examples described later as a swelling evaluation of the coating film is in the range of 0.5 to 5 mL on the coating film. Then, the solution was dropped at room temperature (drop test), allowed to stand for 10 minutes, and evaluated to visually determine the swelling property of the coating film.
Furthermore, in Examples 12 and 13, recoating was performed by applying the same coating composition again on the coating film. If the coating swells more than necessary or peels off, it cannot be overcoated, but in Examples 12 and 13, the coating composition can be overcoated, and there is no practical problem. there were.

[Measurement of hydroxyl value and number average molecular weight of polycarbonate diol]
The hydroxyl value of polycarbonate diol was measured by the following method.
Using a measuring flask, pyridine was added to 12.5 g of acetic anhydride to prepare 50 mL of an acetylating reagent.
A sample for measurement was precisely weighed in an amount of 2.5 to 5.0 g and placed in a 100 mL eggplant-shaped flask.
An acetylating reagent (5 mL) and toluene (10 mL) were added to the eggplant-shaped flask using a whole pipette, and then a condenser tube was attached and heated and stirred at 100 ° C. for 1 hour.
Further, 2.5 mL of distilled water was added to the eggplant-shaped flask using a whole pipette, and the mixture was further heated and stirred for 10 minutes.
After cooling for 2-3 minutes, 12.5 mL of ethanol was added, and 2-3 drops of phenolphthalein was added as an indicator. Then, it titrated with 0.5 mol / L ethanolic potassium hydroxide.
On the other hand, as a blank test, 5 mL of an acetylating reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL eggplant flask and stirred for 10 minutes, and then titrated in the same manner.
Based on these results, the hydroxyl value of the polycarbonate diol was calculated by the following formula (1).

The terminals of the polycarbonate diol used in Examples and Comparative Examples described later were confirmed to be substantially all hydroxyl groups by measurement of ¹³ C-NMR (270 MHz).

Furthermore, the acid value in the polycarbonate diol was measured by titration with KOH, and all of the polymers produced in Examples and Comparative Examples described later had an acid value in the polycarbonate diol of 0.01 or less.
Therefore, the number average molecular weights of the polymers produced in Examples and Comparative Examples described later were obtained by the following formula (2) using the above hydroxyl value.

[Equation 2]
Number average molecular weight = 2 / (hydroxyl value × 10 ⁻³ /56.11) (2)

[Measurement of composition ratio of polycarbonate diol]
1 g of a sample was taken into a 100 mL eggplant flask, 30 g of ethanol and 4 g of potassium hydroxide were added, and reacted at 100 ° C. for 1 hour.
After cooling to room temperature, 2-3 drops of phenolphthalein were added to the indicator and neutralized with hydrochloric acid.
After cooling in the refrigerator for 1 hour, the precipitated salt was removed by filtration and analyzed by gas chromatography.
The analysis was performed by using gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID.
The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.
Based on the obtained results, the composition of 2-butyl-2-ethyl-1,3-propanediol of polycarbonate diol PC-01, which will be described later, using the following formulas (3-1) to (3-3) The composition of 2-methyl-1,3-propanediol of PC-02 and the composition of 1,5-pentanediol of PC-03 were determined.
In addition, when two or more diols are used in combination, and the polycarbonate diol has an ether bond in the molecule, the content is an ether bond with respect to the number of moles of all diols obtained by the above method as a ratio. It was noted as the number of moles (mol%) of the diol having

PC-01
Composition (mol%) = (D1 / E1) × 100 (3-1)
D1: Number of moles of 2-butyl-2-ethyl-1,3-propanediol
E1: Number of moles of all diols PC-02
Composition (mol%) = (D2 / E2) × 100 (3-2)
D2: Number of moles of 2-methyl-1,3-propanediol
E2: Number of moles of all diols PC-03
Composition (mol%) = (D1 / E1) × 100 (3-3)
D3: Number of moles of 1,5-pentanediol
E3: moles of all diols

〔material〕
The raw materials used in the examples and comparative examples are as follows.
(Polycarbonate diol PC)
<Preparation Example 1 of Polycarbonate Diol (PC-01)>
To a 2 L separable flask equipped with a stirrer, a thermometer, and a vacuum jacketed Oldershaw with a reflux head at the top, 330 g (2.1 mol) 1,6- of 2-butyl-2-ethyl-1,3-propanediol was added. 700 g (5.9 mol) of hexanediol was charged.
0.10 g of titanium tetrabutoxide was added as a catalyst, and the mixture was stirred and heated at normal pressure.
The reaction was carried out at a reaction temperature of 140 ° C. to 150 ° C. and a pressure of 3.0 to 5.0 kPa for 20 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate.
Thereafter, the pressure was reduced to 0.5 kPa, and the reaction was further carried out at 150 to 160 ° C. for 10 hours while distilling off ethylene carbonate and the diol to obtain a polycarbonate diol (PC-01).
The polycarbonate diol thus obtained had a hydroxyl value of 140.5, a number average molecular weight of 1980, and the proportion of 2-butyl-2-ethyl-1,3-propanediol was 20 mol%.

<Preparation Example 2 of Polycarbonate Diol (PC-02)>
The same apparatus as that used in Preparation Example 1 for polycarbonate diol described above was used.
After charging 350 g (3.9 mol) of 2-methyl-1,3-propanediol, 300 g (3.3 mol) of 1,4-butanediol and 640 g (7.3 mol) of ethylene carbonate, stirring and dissolving at 70 ° C., Titanium tetrabutoxide 0.064g was added as a catalyst, and it heated with the oil bath set to 175 degreeC.
The reaction was carried out for 20 hours while distilling off a portion of the mixture of ethylene glycol and ethylene carbonate produced at a reflux ratio of 4 from the reflux head at an internal temperature of 130 ° C. and a vacuum of 1.0 to 1.5 kPa. went.
The reflux ratio is represented by reflux amount: distillation amount, and a reflux ratio of 4 refers to 4 refluxs and 1 outflow.
After that, the Oldershaw was replaced with a simple distillation apparatus, heated in an oil bath at 180 ° C, the flask internal temperature was 140-150 ° C, the vacuum was reduced to 0.5 kPa, and residual diol and ethylene carbonate in the separable flask were removed. did.
Thereafter, the setting of the oil bath was raised to 185 ° C., and the reaction was further performed for 5 hours while removing the produced diol at an internal temperature of the flask of 155 to 160 ° C. to prepare polycarbonate diol.
By this reaction, a viscous liquid was obtained at room temperature.
This viscous liquid was designated as polycarbonate diol (PC-02).
The obtained polycarbonate diol had a hydroxyl value of 138.5, a number average molecular weight of 810, and a ratio of 2-methyl-1,3-propanediol of 52 mol%.

<Preparation Example 3 of Polycarbonate Diol (PC-03)>
360 g (3.5 mol) of 1,5-pentanediol, 420 g (3.6 mol) of 1,6-hexanediol, and 640 g (7.3 mol) of ethylene carbonate were charged.
The other conditions were the same as those described above in <Preparation Example 2 for Polycarbonate Diol> to produce polycarbonate diol.
The polycarbonate diol was designated as polycarbonate diol (PC-03).
The polycarbonate diol thus obtained had a hydroxyl value of 139.5, a number average molecular weight of 804, and the proportion of 1,5-pentanediol was 48 mol%.

<Preparation example of terminal alkoxysilylated polycarbonate (PC-04)>
In a 500 mL glass flask equipped with a rectifying column packed with an ordered packing and a stirrer, 55.46 g of 3-isocyanatopropyltriethoxysilane and 94.00 g of the above-described polycarbonate diol (PC-02) (reaction) Ratio: NCO / OH = 0.95) 0.380 g of dibutyltin dilaurate / toluene solution (corresponding to 50 ppm as dibutyltin dilaurate) was added and stirred at 150 rpm while heating at a temperature of 70-80 ° C. under normal pressure. After the reactor internal temperature reached 70 ° C., the reaction was carried out at a constant temperature for 150 minutes.
The contents were subjected to IR analysis to confirm that there were no residual isocyanate groups, and cooled to room temperature to obtain terminal alkoxysilylated polycarbonate.
The obtained terminal alkoxysilylated polycarbonate was used as terminal Si-modified polycarbonate (PC-04).

(Tetraalkoxysilane)
Tetramethoxysilane (TMOS), manufactured by Tokyo Chemical Industry Co., Ltd. Tetraethoxysilane (TEOS), manufactured by Tokyo Chemical Industry Co., Ltd.

(Trialkoxysilane)
Phenyltrimethoxysilane (PhTMOS), manufactured by Tokyo Chemical Industry Co., Ltd. Phenyltriethoxysilane (PhTEOS), manufactured by Tokyo Chemical Industry Co., Ltd.

(Polysiloxane oligomer)
Polysiloxane oligomer (PhOligomer)
Polysiloxane oligomer (1): molecular weight, about 1400, ratio of methyl group to phenyl group is less than 1 polysiloxane oligomer (2): molecular weight, about 1800, ratio of methyl group to phenyl group is 1 or more

(catalyst)
H ₂ O
HNO ₃

(Accelerator (metal catalyst), solvent)
Ti
Hereinafter, Tokyo Chemical Industry Co., Ltd., solvent 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 1,6-hexanediol glycerin 1-methoxy-2-propanol ethylene glycol monobutyl ether ethylene glycol monobutyl ether acetate Diethylene glycol monobutyl ether Propylene glycol monobutyl ether Dipropylene glycol monobutyl ether Ethyl acetate Ethyl butyl Toluene Xylene Tetrahydrofuran Acetone Methanol Ethanol

[Example 1]
To 5 mol of 1-methoxy-2-propanol, 0.01 mol of nitric acid and 4 mol of water were added and stirred for 15 minutes.
Next, 1.5 g of tetramethoxysilane and 0.5 g of polysiloxane oligomer (1) (weight average molecular weight is about 1400) were added and stirred for about 1 hour.
Thereafter, 1.0 g of phenyltrimethoxysilane was added and stirred for 12 hours or more to obtain a phenyltrimethoxysilane mixed solution.
Next, in another container, 10% by mass of polycarbonate diol (PC-01) and 5 mol of 1-methoxy-2-propanol with respect to the total amount of the alkoxysilane (here, the amount of phenyltrimethoxysilane) Was dissolved to obtain the (PC-01) solution.
The (PC-01) solution was added to the phenyltrimethoxysilane mixed solution obtained as described above and stirred for 30 minutes to obtain a coating composition for polycarbonate resin.
In all the stirring processes, the temperature was controlled at 55 to 75 ° C. and mixed by heating.
Next, the above polycarbonate resin coating composition is applied to a predetermined polycarbonate resin substrate (2 mm thickness or 0.12 mm thickness) with a bar coater of No. 300 or less, and heated at 120 ° C. for 2 hours to obtain a polycarbonate resin coating. A test piece (coating material) on which a film was formed was obtained.
Table 1 below shows the appearance evaluation of the coating material, the thickness of the coating film, the presence or absence of cracks, pencil hardness (for each substrate), the bending resistance diameter of the coating material, and the cross-cut test result.

[Example 2]
Instead of polycarbonate diol (PC-01), polycarbonate diol (PC-02) was used.
Other conditions were the same as in [Example 1] above, and a polycarbonate resin coating composition was produced, and the coating film and the coating were tested and evaluated.

Example 3
The thickness of the coating film was set to two-thirds of the above [Example 2].
Other conditions were the same as in [Example 2] above, and a polycarbonate resin coating composition was produced, and the coating film and the coating were tested and evaluated.

Example 4
The amount of phenyltrimethoxysilane (PhTMOS) and the amount of polysiloxane oligomer (PhOligomer) were the amounts shown in Table 1 below. Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 5
The amounts of tetramethoxysilane (TMOS) and phenyltrimethoxysilane (PhTMOS) were shown in Table 1 below. Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 6
Instead of polycarbonate diol (PC-02), polycarbonate diol (PC-03) was used. Other conditions were the same as in [Example 5], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 7
The amount of titanium catalyst shown in Table 1 below was used.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 8
The amounts of tetramethoxysilane, phenyltrimethoxysilane, and polysiloxane oligomer were the amounts shown in Table 1 below.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 9
Tetramethoxysilane was changed to tetraethoxysilane.
Also, phenyltrimethoxysilane was changed to phenyltriethoxysilane.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 10
As the polysiloxane oligomer, a polysiloxane oligomer (2) having a weight average molecular weight of about 1800 and a methyl group amount of about 10% was used.
The amount of catalyst was set to the amount shown in Table 1 below.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 11
As the polycarbonate diol, terminal Si-modified polycarbonate diol (PC-04) was used. The amount of catalyst was set to the amount shown in Table 1 below.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 12
The film thickness of the coating film was set to two-thirds of the above [Example 2].
A coating composition for polycarbonate resin was produced, and then this was applied to a polycarbonate resin substrate (2 mm or 0.12 mm thick) with a No. 300 bar coater to obtain a heating condition at 120 ° C. 12 It was time.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.
In Examples, Example 12 was the best overall in terms of pencil hardness, flex resistance, cross-cut test, solvent resistance test, and recoatability on polycarbonate and glass substrates.

Example 13
The thickness of the coating film was set to two-thirds of the above [Example 2].
A coating composition for polycarbonate resin is manufactured, and then this is applied to a polycarbonate resin substrate (2 mm or 0.12 mm thick) with a No. 300 bar coater, and the heating conditions for obtaining a test piece through heat treatment are as follows. And 140 ° C. for 12 hours.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

Example 14
The content of the polycarbonate diol (PC-02) contained in the coating film was 15% by mass with respect to the alkoxysilane, and the film thickness was 2/3 of the above [Example 2].
A coating composition for polycarbonate resin is manufactured, and then this is applied to a polycarbonate resin substrate (2 mm or 0.12 mm thick) with a No. 300 bar coater, and the heating conditions for obtaining a test piece through heat treatment are as follows. 140 ° C. for 12 hours.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 1]
The amounts of tetramethoxysilane and polysiloxane oligomer were shown in Table 1.
No phenyltrialkoxysilane was used.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 2]
The amounts of tetramethoxysilane, phenyltrimethoxysilane, and catalyst were the amounts shown in Table 1.
No polysiloxane oligomer was used.
Other conditions were the same as in [Example 2], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 3]
As the polycarbonate diol, terminal Si-modified polycarbonate (PC-04) was used.
The other conditions were the same as in [Comparative Example 2], that is, a polysiloxane oligomer was not used, a polycarbonate resin coating composition was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 4]
Tetraethoxysilane was used instead of tetramethoxysilane.
Instead of phenyltrimethoxysilane, phenyltriethoxysilane was used.
The other conditions were the same as in [Comparative Example 2], that is, a polysiloxane oligomer was not used, a polycarbonate resin coating composition was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 5]
(PC-03) was used as the polycarbonate diol.
Other conditions were the same as in [Comparative Example 4], that is, a polysiloxane oligomer was not used, a polycarbonate resin coating composition was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 6]
The amounts of tetramethoxysilane, phenyltrimethoxysilane, polysiloxane oligomer, and catalyst were shown in Table 1 below.
No polycarbonate diol was used.
Other conditions were the same as in [Example 1], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

[Comparative Example 7]
The amounts of tetramethoxysilane, phenyltrimethoxysilane, polysiloxane oligomer, and catalyst were shown in Table 1 below.
No polycarbonate diol was used.
A coating composition for polycarbonate resin is manufactured, and then this is applied to a polycarbonate resin substrate (2 mm or 0.12 mm thick) with a No. 300 bar coater, and the heating conditions for obtaining a test piece through heat treatment are as follows. 140 ° C. for 12 hours.
Other conditions were the same as in [Example 1], and a coating composition for polycarbonate resin was produced, and the coating film and the coating were tested and evaluated.

For Examples 3, 12, and 13, the drop test of 1-methoxy-2-propanol was observed and evaluated in more detail with the passage of time in more detail at room temperature.
The result was that the coating film of Example 3 swelled relatively quickly, the coating film of Example 12 swelled in a few minutes, and the coating film of Example 13 did not swell.

  As shown in Table 1, it can be seen that the coating compositions of Examples 1 to 14 have good adhesion to polycarbonate resin, coating film hardness, flex resistance, and practically sufficient hardness. It was.

  The coating composition of the present invention has industrial applicability as a coating material for plastic lenses and electronic / electrical materials.

Claims (10)

Polycarbonate diol,
Tetraalkoxysilane,
Trialkoxysilane,
A polysiloxane oligomer;
A coating composition for polycarbonate resin.   The coating composition for polycarbonate resin according to claim 1, wherein the polysiloxane oligomer contains an aromatic ring or an alicyclic cyclic compound.   The coating composition for polycarbonate resin according to claim 1, further comprising a metal complex.   The coating composition for polycarbonate resin according to any one of claims 1 to 3, wherein the polysiloxane oligomer has a weight average molecular weight of 300 to 1980. The polysiloxane oligomer;
The mass ratio with the sum of the tetraalkoxysilane and trialkoxysilane is
The coating composition for polycarbonate resin according to claim 1, wherein polysiloxane oligomer: (tetraalkoxysilane + trialkoxysilane) = 1: 10 to 1: 1. Further comprising a medium,
The total mass of the tetraalkoxysilane, the trialkoxysilane, and the polysiloxane oligomer, and the mass ratio of the medium,
(Tetraalkoxysilane + trialkoxysilane + polysiloxane oligomer): Coating composition for polycarbonate resin according to any one of claims 1 to 5, wherein medium = 1: 2-30.   The coating composition for polycarbonate resin according to any one of claims 1 to 6, wherein the tetraalkoxysilane and / or the trialkoxysilane has a methoxy group.   The coating composition for polycarbonate resin according to any one of claims 1 to 7, wherein the trialkoxysilane includes an aromatic ring or an alicyclic cyclic compound.   A coated product obtained by coating a polycarbonate resin substrate with the coating composition for polycarbonate resin according to any one of claims 1 to 8.   The coated product according to claim 9, which is heat-treated after the coating.