WO2014104195A1

WO2014104195A1 - Adhesion-improving agent and silane compound

Info

Publication number: WO2014104195A1
Application number: PCT/JP2013/084892
Authority: WO
Inventors: 一樹上村; 秀樹片江
Original assignee: 大阪有機化学工業株式会社
Priority date: 2012-12-28
Filing date: 2013-12-26
Publication date: 2014-07-03
Also published as: TWI598355B; TW201441239A; KR20150103102A; JP6267132B2; KR102137626B1; CN104937054A; JPWO2014104195A1; CN104937054B

Abstract

The present invention provides an adhesion-improving agent which has an adhesion-improving property and is stable. The adhesion improving agent is characterized by comprising a silane compound which is a reaction product of an isocyanate-containing silicon compound represented by general formula (1) with a silicon compound represented by general formula (2). The present invention also provides a novel silane compound represented by general formula (3') or (4').

Description

Adhesion improver and silane compound

The present invention relates to an adhesion improver. The present invention also relates to a novel silane compound.

In recent years, in the field of electronic and optical materials, high-definition, wide viewing angle, high image quality of flat panel displays using liquid crystal, organic EL, etc., high brightness of light sources using light semiconductors such as light emitting diodes (LEDs) Improvements such as shortening the wavelength, whitening, increasing the frequency of electronic circuits, and improving the performance of optical and electronic components such as circuits and communications using light are being promoted. In the semiconductor technical field, electronic devices are rapidly becoming smaller, lighter, higher performance, and multifunctional. In addition, an optical circuit using an optical waveguide or the like that enables higher-speed processing has been studied. Corresponding to these, higher density and higher wiring of the wiring board are required.

For example, the number of pixels of a display is increasing to 4k2k etc. with the high definition and high image quality of a flat panel display. For this reason, it is necessary to create a fine pattern.

Also, in order to increase the density and the wiring of a wiring board, a photoresist material having high photosensitivity, high heat resistance, and chemical resistance is required.

In touch panel displays, the use of capacitive touch panels has increased in recent years. The capacitance type touch panel captures a change in capacitance between the fingertip and the conductive film and searches for a position. In a capacitive touch panel, a layer for reducing external impact cannot be provided unlike a resistive touch panel. For this reason, high hardness is required for the surface protective layer.

In order to obtain products that meet the above requirements, the materials used must have high adhesion, in addition to high photosensitivity, high heat resistance, chemical resistance, hardness, and other properties. However, sufficient adhesion cannot be obtained with current materials.

It has been practiced to improve adhesion by adding a silane coupling agent to the material (for example, see Patent Document 1). However, there is a problem that the adhesiveness cannot be improved sufficiently. Moreover, there exists a problem that adhesiveness and stability are not compatible.

In order to improve the stability, attempts have been made to block the isocyanate of the silane coupling agent (see, for example, Patent Documents 2 and 3). However, the blocking agent described in this document has a problem that the stability is insufficient and the adhesiveness is lowered. Moreover, the blocking agent which blocked the isocyanate is eliminated. There is a problem in that the liquid crystal panel is burned by leaving the detached blocking agent.

JP 2001-33955 A JP 2001-135224 A JP 2009-161830 A

That is, the present invention has been made in view of the above problems, and an object thereof is to provide a stable adhesion improving agent having adhesion improving properties and a novel silane compound.

As a result of intensive studies to solve the above problems, the present inventors have found that a silane compound, which is a reaction product of a silicon compound having an isocyanate and a silicon compound having a specific block group, has adhesion improving properties and is stable. Further, the inventors have found a novel silane compound in the reaction product and completed the present invention. That is, the present invention is as follows.

The adhesion improving agent of the present invention contains a silane compound that is a reaction product of a silicon compound having an isocyanate represented by the following general formula (1) and a silicon compound represented by the following general formula (2).

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. Is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms and may contain a divalent or trivalent linking group, and q is an integer of 1 to 3. r is an integer of 1 to 3.)

(Wherein R ⁴ to R ⁶ may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. B is a substituted or unsubstituted carbon group having 2 carbon atoms. A linear or branched alkylene group of ˜15 and may contain a divalent linking group, p is an integer of 0 or 1. X is O, NH, NH—CO—NH, S. s is an integer of 1 to 3. t is an integer of 1 to 3. However, when p = 0, s = 1 and t = 1.)

In the adhesion improver of the present invention, the silane compound is preferably a compound represented by the following formula (3) or (4).

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ⁴ to R ⁶ may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and A represents a substituted or unsubstituted straight chain having 2 to 18 carbon atoms. Or a branched alkylene group which may contain a divalent or trivalent linking group, and B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms; X may be O, NH, NH—CO—NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3. )

In the adhesion improver of the present invention, in the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group represented by A, the divalent or trivalent linking group has the following formula: In the linear or branched alkylene group having 2 to 15 carbon atoms and having a linking group, which is at least one selected from the group consisting of [A1] and represented by B, It is preferably at least one selected from the group consisting of formula [B1].

[R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, —CH═,

(R ⁹ and R ¹⁰ are alkyl groups having 1 to 5 carbon atoms, m3 is an integer of 1 to 5),

(M4 is an integer from 1 to 5),

(R ¹¹ is an alkyl group having 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane having 3 to 6 carbon atoms which may have a substituent. When a divalent group is bonded to either R ⁷ or R ⁸ , the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms and having at least two bonds,

In the adhesion improver of the present invention, the silane compound is preferably a silane compound represented by any one of the following formulas (5) to (8).

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ⁴ to R ⁶ may be the same or different and each represents an alkyl group of 1 to 5. m is an integer of 2 to 18.)

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ⁴ to R ⁶ may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to (It is an integer of 15.)

The adhesion improving agent of the present invention preferably further contains a silane compound represented by the following general formula (9).

[Wherein R ¹² to R ¹⁴ may be the same or different and each represents hydroxy or an alkoxy group having 1 to 5 carbon atoms; R ¹⁵ represents a carboxylic anhydride group or —CHR ¹⁶ COOH (wherein R ¹⁶ Is a carboxylic anhydride, carboxylic acid or carboxylic ester group), and D is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted carbon number. An alkylene group having 2 to 10 linear or branched at least one double bond; ]

The present invention also relates to a resist material containing the adhesion improving agent.

The present invention further relates to a novel silane compound represented by the following general formula (3 ′) or (4 ′).

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ⁴ to R ⁶ may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and A represents a substituted or unsubstituted straight chain having 2 to 18 carbon atoms. Or a branched alkylene group which may contain a divalent or trivalent linking group, and B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms; X is O or NH—CO—NH, p is an integer of 0 or 1. q is an integer of 1 to 3. r is 1 S is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3.)

In the silane compound represented by the general formula (3 ′) or (4 ′) of the present invention, in the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group represented by A, 2 The valent or trivalent linking group is preferably at least one selected from the group consisting of the following formula [A1], and is a straight chain having 2 to 15 carbon atoms having a linking group represented by B or In the branched alkylene group, the divalent linking group is preferably at least one selected from the group consisting of the following formula [B1].

(M4 is an integer from 1 to 5),

The silane compound represented by the general formula (3 ′) or (4 ′) of the present invention is preferably a silane compound represented by the following general formula (10).

In the formula, R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. ⁴ to R ⁶ may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to And is an integer of 15. X is O or NH—CO—NH.

The adhesion improver of the present invention is a silane compound that is a reaction product of a silicon compound having an isocyanate and a silicon compound having a specific block group. By using this compound together with a resist material or the like, adhesion and stability can be imparted to the resist material or the like. Moreover, when the resist material to which the adhesion improving agent of the present invention is added is used, a device having characteristics such as high definition, high image quality, high performance, high density, and high wiring can be manufactured.

The novel silane compound of the present invention can impart adhesion and stability to a resin, paint, resist material, coating agent, etc. when used in combination with a resin, paint, resist material, coating agent, or the like. In addition, the molded product produced by adding the silane compound of the present invention can avoid the occurrence of seizure or the like.

FIG. 1 is an IR chart showing the completion of the reaction in Example 1. FIG. 2 is an NMR chart of the reaction product of Example 1.

(Adhesion improver)
The adhesion improving agent of the present invention is a silane compound that is a reaction product of a silicon compound having an isocyanate and a silicon compound having a specific block group. Specifically, it is as follows.

The compound represented by the general formula (1) is a compound containing q silicon-containing groups and r isocyanate groups in the molecule.

In the above formula (1), R ¹ to R ³ may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. is there.

Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-methylpropoxy group, 2-butoxy group, 1,1-dimethylethoxy. Group, 1-pentoxy group, 3-methylbutoxy group, 2,2-dimethylpropoxy group, 1,1-dimethylpropoxy group and the like, preferably methoxy group and ethoxy group.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-methylpropyl group, 2-butyl group, and 1,1-dimethylethyl. Group, 1-pentyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, and the like, preferably methyl group and ethyl group.

A is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms. The carbon number of the linear or branched alkylene group is preferably 2 to 12, more preferably 2 to 6. Examples of the substituent of a linear or branched alkylene group having 2 to 18 carbon atoms include an ester group to which an alkyl group having 1 to 5 carbon atoms is bonded. A may contain at least one divalent or trivalent linking group. Examples of the divalent or trivalent linking group include those represented by the following formula [A1]. When the substituted or unsubstituted C2-C18 linear or branched alkylene group contains a trivalent linking group, a compound in which q and r are integers greater than 1 in the formula (1) is obtained. It is done.

(M4 is an integer from 1 to 5),

In the above [A1], the alkyl group having 1 to 5 carbon atoms is the same as that exemplified in the general formula (1). Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, benzyl group, and tolyl group. Examples of the cycloalkane having 3 to 6 carbon atoms include cyclopropane, cyclobutane, cyclopentane, and cyclohexane.

The isocyanate group or silicon atom is bonded to A. When A contains one or more trivalent linking groups [A1], a compound having a plurality of isocyanate groups in the molecule or a compound containing a plurality of silicon atoms in the molecule can be obtained. Even when a trivalent linking group is included, a divalent linking group is formed by bonding a group that does not participate in the reaction, such as a methyl group or a cyano group, to the end of the one linking group. In some cases.

Q is an integer of 1 to 3, preferably 1. r is an integer of 1 to 3, preferably 1.

The compound represented by the general formula (2) is a compound having s groups containing silicon and t XH groups in the molecule.

R ⁴ to R ⁶ may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. Examples of the alkoxy group having 1 to 5 carbon atoms or the alkyl group having 1 to 5 carbon atoms are the same as those exemplified above for R ¹ to R ³ .

B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms. The number of carbon atoms of the linear or branched alkylene group is preferably 2 to 10, more preferably 2 to 6. B may contain at least one divalent linking group. Examples of the divalent linking group include those represented by the following formula [B1].

X is O, NH, NH—CO—NH, S.

X group or silicon atom is bonded to B, or X group and silicon atom are directly bonded. In those having a plurality of X groups in the molecule, the second or more X groups are bonded to the above [B1], or the substituent [B1] itself is an NH—CO—NH group. In the case of a molecule having a plurality of silicon atoms in the molecule, the second or more silicon atoms are bonded to the above [B1] or are a substituent of a linear or branched alkylene group.

P is an integer of 0 or 1. s is an integer of 1 to 3, and is preferably 1. t is an integer of 1 to 3, and is preferably 1.

(Silane compound)
The silane compound according to the present invention is a reaction product of a silicon compound having an isocyanate represented by the general formula (1) and a silicon compound represented by the general formula (2).

This reaction is a nucleophilic addition reaction of the X group of the silicon compound represented by the general formula (2) to the isocyanate group of the silicon compound having an isocyanate represented by the general formula (1). In the present invention, the reaction product may have all isocyanate groups blocked with X groups. That is, it may be a reaction product of a silicon compound having a plurality of isocyanate groups and a silicon compound having a plurality of X groups.

This reaction can be carried out without a catalyst. The solvent may or may not be used, and is not particularly limited. When using a solvent, for example, ethers such as diethyl ether, ethyl methyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and dichloromethane, amides such as dimethylformamide, ethyl acetate, methyl acetate, butyl acetate and the like Esters, N-methylpyrrolidone and the like can be used.

The use ratio of the silicon compound having the isocyanate represented by the general formula (1) and the silicon compound represented by the general formula (2) is completely different from X of the silicon compound in which the isocyanate is represented by the general formula (2). If it can respond to, there will be no restriction | limiting in particular. The amount of X used may be large or small relative to 1 mole of isocyanate. When the amount of X used is large relative to 1 mole of isocyanate, a compound represented by formula (3) or (4) is obtained. When the amount of X used is small relative to 1 mole of isocyanate, active hydrogen in the silicon compound represented by the general formula (3) or (4) remains in the reaction system. By reacting, a compound having a structure in which the isocyanate group disappears is obtained.

The use ratio of the silicon compound having the isocyanate represented by the general formula (1) and the silicon compound represented by the general formula (2) is particularly limited as long as the isocyanate completely reacts with X of the silicon compound. There is no. For example, X is 1.00 to 6.00 moles, preferably 1.00 to 1.50 moles, more preferably 1.00 to 1.20 moles per mole of isocyanate. If X is less than 1.00 mol with respect to 1 mol of isocyanate, the reaction between isocyanate and X cannot be carried out completely, which is not preferable. When X is more than 6.00 moles with respect to 1 mole of isocyanate, an unreacted silicon compound represented by the general formula (2) remains, which is not preferable.

The reaction temperature is 30 to 90 ° C, preferably 40 to 80 ° C, more preferably 50 to 70 ° C. The reaction time is usually 1 minute to 2 days, particularly 30 minutes to 3 hours.

The reaction is completed by confirming the disappearance of the isocyanate peak (2200 to 2300 cm ⁻¹ ) using infrared spectroscopy (hereinafter referred to as “IR”).

The silane compound which is a reaction product of the silicon compound having an isocyanate represented by the general formula (1) and the silicon compound represented by the general formula (2) is, for example, the following formula (3) or (4) It is preferable that it is a compound represented by these.

The silane compound represented by the following general formula (3) is a silicon compound having an isocyanate represented by the above general formula (1), and has r (r = integer of 1 to 3) isocyanates. In the silicon compound represented by (2), it is a reaction product having one X, that is, t = 1.

In the formula, R ¹ to R ³ , R ⁴ to R ⁶ , A, B, X, p, q, r, and s are the same as those shown in the general formulas (1) and (2).

The silane compound represented by the general formula (3) is obtained by the following reaction formula.

The silane compound represented by the following general formula (4) has one isocyanate (r = 1) in the silicon compound having an isocyanate represented by the above general formula (1), and the above general formula (2) It is a reaction product in the case where the silicon compound represented has t (t = 1 to 3).

In the formula, R ¹ to R ³ , R ⁴ to R ⁶ , A, B, X, p, q, s, and t are the same as those shown in the general formulas (1) and (2).

The silane compound represented by the general formula (4) is obtained by the following reaction formula.

More preferably, the silane compound is a silane compound represented by any one of the following formulas (5) to (8).

In the formula, R ¹ to R ³ are the same as those shown in the chemical formula (1). R ⁴ to R ⁶ may be the same or different and are 1 to 5 alkyl groups. The alkyl group having 1 to 5 carbon atoms is the same as described above. m is an integer of 2 to 18, preferably 2 to 8, particularly preferably an integer of 2 to 4.

In the formula, R ¹ to R ³ and R ⁴ to R ⁶ are the same as those shown in the chemical formulas (1) and (2). m is the same as described above. n is an integer of 2 to 15, preferably 2 to 8, particularly preferably an integer of 2 to 4.

In the formula, R ¹ to R ³ , R ⁴ to R ⁶ , m, and n are the same as those in the general formula (6).

The adhesion improver of the present invention can be used by adding to a material used for applications requiring adhesion and stability. Specifically, it may be used by adding to a resist material, a passivation film, an overcoat agent, an insulating film material, OP varnish, ink, or the like.

The adhesion improver of the present invention can further contain a silane compound represented by the following general formula (9).

[Wherein R ¹² to R ¹⁴ may be the same or different and each represents hydroxy or an alkoxy group having 1 to 5 carbon atoms; R ¹⁵ represents a carboxylic anhydride group or —CHR ¹⁶ COOH (where R ¹⁶ represents D is a substituted or unsubstituted C2-C10 linear or branched alkylene group, or a substituted or unsubstituted carbon, or a carboxylic anhydride group, a carboxylic acid group or a carboxylic acid ester group. It is an alkylene group having at least one double or straight chain or branched chain having a number of 2 to 10. ]

In the above formula (9), R ¹² to R ¹⁴ may be the same or different and are hydroxy or an alkoxy group having 1 to 5 carbon atoms.

In the above formula (9), the alkoxy group having 1 to 5 carbon atoms is the same as that shown in the above formula (1), and a methoxy group or an ethoxy group is preferable.

In the above formula (9), R ¹⁵ is a carboxylic anhydride group or —CHR ¹⁶ COOH (wherein R ¹⁶ is a carboxylic anhydride group, a carboxylic acid group or a carboxylic ester group), and a carboxylic anhydride group It is preferable that

Examples of the carboxylic anhydride constituting the carboxylic anhydride group include succinic anhydride, maleic anhydride, and glutaric anhydride, and succinic anhydride is preferable.

The carboxylic acid ester group is not particularly limited, and examples thereof include a linear or branched ester group with a C 1-5 alcohol, a polyethylene chain, a polypropylene chain, and the like, and a (meth) acryloyloxy group. It may have a reactive group such as a (meth) acrylamide group.

In the above formula (9), D is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted linear or branched chain group having 2 to 10 carbon atoms. An alkylene group having two double bonds, and the alkylene chain preferably has 2 to 5 carbon atoms, more preferably 2 or 3.

Specific examples of the general formula (9) include trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, triethoxysilylbutyl succinic anhydride, 3- [6- (tri Trimethoxysilylhexynyl succinic anhydride such as methoxysilyl) -2-hexen-1-yl] succinic anhydride, 2-methyl-3- (triethoxysilyl) propyl succinic anhydride, 3- [10- (trimethoxy Silyl) -2-decen-1-yl] succinic anhydride, tetrahydro-2,5-dioxo-α- [2- (triethoxysilyl) ethyl] -3-furan acetic acid, 3-trimethoxysilylpropyl glutaric anhydride , 3-triethoxysilylpropyl glutaric anhydride and hydrolysates thereof, and the like. Shi silyl propyl succinic anhydride are preferable.

When the compound of the general formula (9) has an acid anhydride group, the ring is opened by moisture in the system to generate a carboxyl group. A scheme in the case where the acid anhydride group is succinic anhydride is shown below, but the same applies to other acid anhydride groups. In the formula, the R ¹⁷ group represents a hydroxyl group derived from a carboxyl group produced by hydrolysis, or an alkoxy group produced by alcoholysis with an alcohol produced in the reaction system by hydrolysis, such as an alcohol having 1 to 5 carbon atoms. Show. Such a ring-opened product is also included in the compound of the general formula (9).

(In the formula, R ¹⁷ represents a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms, and the alkoxy group having 1 to 5 carbon atoms is the same as that represented by the above formula (1).)

The adhesiveness-improving agent of the present invention can further improve the adhesiveness by including the silane compound represented by the general formula (9).

[Resist material]
When the adhesion improver of the present invention is added to a resist material and used, it can be used as a protective film (resist) when processing such as sand blasting, ion implantation, etching, etc. in various manufacturing processes. Since the resist material to which the adhesion improver of the present invention is added is excellent in adhesion and developability, it is possible to produce a highly functional device. The resist may be a negative resist or a positive resist. The addition amount at the time of adding the adhesion improving agent of the present invention to the resist material is not particularly limited, and may be appropriately determined according to the material such as the resist material and the purpose of use.

The resist material usually contains a polymerizable compound (monomer or oligomer), a binder polymer, a surfactant, a photopolymerization initiator, a solvent, and the like. Moreover, you may add an inorganic filler, a ultraviolet absorber, dye, a pigment, etc. as needed. The adhesion improver of the present invention is used by adding to such a resist material.

(Polymerizable compound)
The resist material of the present invention contains at least one polymerizable compound (monomer or oligomer) having at least two ethylenically unsaturated bonds. The polymerizable compound having at least one ethylenically unsaturated bond is not particularly limited as long as it is capable of radical polymerization. The polymerizable compound only needs to have at least one ethylenically unsaturated bond, for example, a compound having one ethylenically unsaturated bond in the molecule and two ethylenically unsaturated bonds in the molecule. Either a compound or a compound having three or more ethylenically unsaturated bonds in the molecule may be used.

Specific examples of the compound having two ethylenically unsaturated bonds in the molecule include a bisphenol A di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and a urethane bond in the molecule. Examples include di (meth) acrylate compounds, polyalkylene glycol di (meth) acrylate compounds, trimethylolpropane di (meth) acrylate, and 1,6-hexanediol diacrylate.

2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, a compound having two ethylenically unsaturated bonds in its molecule, is BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) Alternatively, it is commercially available as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (new It is commercially available as a product name of Nakamura Chemical Co., Ltd.

The compound having two ethylenically unsaturated bonds in the molecule is used alone or in any combination of two or more.

Examples of the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters.

Nonylphenoxypolyethyleneoxyacrylate includes nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate Nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, nonylphenoxyundecaethyleneoxyacrylate, and the like. These may be used alone or in any combination of two or more.

Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethyl-o- Phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, and the like, among others, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate Is preferred. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.). These can be used alone or in combination of two or more.

Examples of the compound having three or more ethylenically unsaturated bonds in the molecule include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (one having a total number of repeating oxyethylene groups of 1 to 5). ), PO-modified trimethylolpropane tri (meth) acrylate, EO and PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These can be used alone or in combination of two or more.

The content of the polymerizable compound in the resist material of the present invention is not particularly limited, but is preferably 30 to 70 parts by mass, and 35 to 65 parts by mass in 100 parts by mass of the total amount of the binder polymer and polymerizable compound described below. More preferably, the amount is 35 to 60 parts by mass. When this content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be obtained, and when it is 70 parts by mass or less, film formability tends to be good, and a good resist shape is obtained. There is a tendency to become easily.

(Binder polymer)
The resist material of the present invention contains at least one binder polymer. As the binder polymer, a commonly used binder polymer can be used without any particular limitation. Specific examples include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. Among these, acrylic resins are preferable from the viewpoint of alkali developability.
A binder polymer can be used individually by 1 type or in combination of 2 or more types.

The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives having a substituent on the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene; acrylamide such as diacetone acrylamide; Esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether; (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid glycidyl ester, 2 , 2,2-trifluoroethyl (meth) acrylate, (meth) acrylic esters such as 2,2,3,3-tetrafluoropropyl (meth) acrylate; (meth) acrylic acid, α-bromoacrylic acid, α-Chloracrylic acid, β-furyl (meth) ac Acrylic acids such as lauric acid and β-styryl (meth) acrylic acid; maleic monoesters such as monoethyl maleate and monoisopropyl maleate; maleic acid, maleic anhydride, monomethyl maleate, fumaric acid, cinnamic acid , Α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These can be used alone or in combination of two or more.

The (meth) acrylic acid alkyl ester may be a compound in which an alkyl group is substituted with a hydroxyl group, an epoxy group, a halogen group or the like.

Examples of the monomer of (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meta ) Acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) ) Aromatic ring-containing (meth) acrylates such as alkyl (meth) acrylates such as decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate , Hydroxy Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyl group-containing, such as hydroxybutyl (meth) acrylate (meth) acrylate, (meth) acrylamide, butoxy methylol (meth) amide group-containing monomers such as acrylamide. These can be used alone or in combination of two or more.

In addition, the binder polymer in the present invention preferably contains a carboxyl group from the viewpoint of alkali developability. The binder polymer containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, (meth) acrylic caprolactone adduct, (meth) acryloylethyl monophthalate, (meth) acryloylethyl monohexahydrophthalate, (meth) Acryloylethyl monotetrahydrophthalate and the like are preferable, and methacrylic acid is more preferable.

These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer.

In the present invention, the ratio of the resin for the binder polymer to the total sum of the resist materials (solid content, the same shall apply hereinafter) is in the range of 20 to 90% by mass, preferably 30 to 70% by mass. The resist pattern formed by exposure and development is 20% by mass or more and 90% by mass or less from the viewpoint that resist characteristics, for example, sufficient resistance and the like in tenting, etching, and various plating processes.

(Photopolymerization initiator)
As a photoinitiator used for the resist material of this invention, it is good to use what contains at least 1 sort (s) of an imidazole dimer as a photoinitiator. Examples of the imidazole dimer as a photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer. 2- (2,4-dichlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3,4-dimethoxyphenyl) imidazole dimer, 2, 5-bis (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-bis (3,4-dimethoxyphenyl) imidazole dimer 2,5-bis (o-fluorophenyl) -4- (3,4-dimethoxyphenyl) imidazole dimer, 2- (o-methoxyphenyl) -4,5-di E sulfonyl imidazole dimer, and 2-(p-methoxyphenyl) -4,5-diphenyl imidazole dimer, etc. of 2,4,5 triaryl imidazole dimer and the like.

In the above example, only symmetrical compounds are illustrated as 2,4,5-triarylimidazole dimers, but asymmetrical compounds in which the substituents of the aryl groups of two 2,4,5-triarylimidazoles are different. It may be. These are used alone or in combination of two or more.

Also, a combination with a pyrazoline compound such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline is a preferred embodiment.

In addition to the compounds shown above, other photopolymerization initiators can be used in combination. Here, the photopolymerization initiator is a compound that is activated by various actinic rays such as ultraviolet rays and starts polymerization. Other photopolymerization initiators include quinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin and benzoin ethers such as benzoin methyl ether and benzoin ethyl ether. Acridine compounds such as 9-phenylacridine, benzyldimethyl ketal, benzyldiethyl ketal, 2,4-trichloromethyl- (4 ″ -methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxy) Naphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, triazines such as 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine, 2-methyl-1 -(4-Methylthiophenyl -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples include fin oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] and the like.

Further, there are also combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds. Further, there are oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferred.

The ratio of the photopolymerization initiator contained in the resist material of the present invention is 0.01 to 30% by mass. If this ratio is less than 0.01% by mass, sufficient sensitivity cannot be obtained. On the other hand, if this ratio exceeds 30% by mass, fogging due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated. The content is more preferably 0.1 to 15% by mass, and further preferably 0.1 to 10% by mass.

(Other additives)
The resist material of the present invention can further contain various additives. Additives include dyes, photochromic agents, thermochromic inhibitors, plasticizers, hydrogen donors, color formers, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, peeling accelerators, An antioxidant, a fragrance | flavor, an imaging agent, a thermal crosslinking agent etc. can be mentioned.

(solvent)
The resist material of the present invention can contain a solvent as necessary. It does not restrict | limit especially as a solvent, It can select suitably from the solvent used normally. Specifically, for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycol acetates such as methyl cellosolve and ethyl cellosolve, hydrocarbons such as toluene, and N, N-dimethylformamide and the like Examples thereof include protic polar solvents, ether acetates such as propylene glycol monomethyl ether 2-acetate and methyl methoxypropionate, and cyclic ketones such as cyclohexanenone.

These solvents are used alone or as a mixed solvent combining two or more kinds. The content of the solvent is appropriately selected according to the purpose. For example, a solution having a solid content of about 30 to 60% by mass can be obtained. The solid content is the total amount of nonvolatile components in the resist material.

[Method for producing resist pattern]
The resist material can be used for forming a resist layer as follows, for example. A resist layer, which is a coating film of the resist material, can be formed on the support by applying the resist material on the surface of a support such as a support film, a metal plate, or glass, which will be described later, and drying.

As the support film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of the metal plate include iron alloys such as copper, copper alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper alloys, iron alloys, and the like.

The thickness of the resist layer to be formed varies depending on its use, but is preferably about 0.1 μm to 100 μm after drying. The surface (surface) opposite to the surface facing the support of the resist layer may be covered with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

In the method for producing a resist pattern using the resist material of the present invention, (i) the photosensitive element is placed on a circuit forming substrate, and the photosensitive resin composition layer in the photosensitive element is in close contact with the circuit forming substrate. And (ii) at least a part of the photosensitive resin composition layer is irradiated with an actinic ray by a direct drawing method to photocure the exposed portion to be photocured. And (iii) a developing step of removing the unexposed portion of the photosensitive resin composition layer from the circuit forming substrate by development, and including other steps as necessary. Composed.

(New silane compound)
The general formula (3), which is a reaction product of the silicon compound having an isocyanate represented by the general formula (1) and the silicon compound represented by the general formula (2) described in the above-described adhesion improver and Among the silane compounds represented by (4), the compounds represented by the following general formulas (3 ′) and (4 ′) in which X is O or NH—CO—NH are novel compounds, It is provided for the first time. By adding the silane compound represented by the general formula (3 ′) or (4 ′) of the present invention to a resin, paint, resist material, coating agent, etc., adhesion and stability can be imparted. .

With respect to the above formulas (3 ′) and (4 ′), all the explanations regarding the formula (3) or (4), including the production method, apply except that X is O and NH—CO—NH. be able to.

The novel silane compound (3 ′) or (4 ′) is preferably a compound represented by the following general formula (10).

Wherein, R ¹ ~ R ³ are the same as R ¹ ~ R ³ in the formula (3 ') or (4').

R ⁴ ~ R ⁶ are the same as R ⁴ ~ R ⁶ in the formula (3 ') or (4').

M is an integer of 2 to 18, preferably 2 to 8, particularly preferably an integer of 2 to 4. n is an integer of 2 to 15, preferably 2 to 8, particularly preferably an integer of 2 to 4. X is the same as in the above formula (3 ') or (4').

Preferred examples of the compound represented by the general formula (10) include compounds represented by the above formulas (5) and (7).

The novel silane compound of the present invention can be used together with resins, paints, resist materials, coating agents and the like. The addition amount is not particularly limited, and may be appropriately determined according to the material such as resin, paint, resist material, coating agent and the purpose of use, and all the explanations given above in the adhesion improver of the present invention are all novel of the present invention. This also applies to the use of silane compounds.

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

(Example 1)
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanatepropyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 485 parts by mass of N-methylpyrrolidone (NMP) were added. 108 parts by mass of ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the mixed liquid while stirring. Thereafter, the mixture was raised to 65 ° C. and reacted for 2 days while maintaining this temperature. Completion of the reaction was confirmed by disappearance of isocyanate peak using IR.
The solid content concentration of the obtained solution was 30.0% by mass.

By the above reaction, a novel compound represented by the following formula was obtained. FIG. 1 is an IR chart showing the completion of the reaction in Example 1. This confirmed that the isocyanate group had disappeared. FIG. 2 is an NMR chart of the reaction product of Example 1.

(Example 2)
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanate propyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 336 parts by mass of N-methylpyrrolidone (NMP) were added. 44 parts by mass of trimethylsilanol (LS-310, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise to the mixed liquid with stirring. Thereafter, the mixture was raised to 65 ° C. and reacted for 2 hours while maintaining this temperature. Completion of the reaction was confirmed by disappearance of isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

By the above reaction, a novel compound represented by the following formula was obtained.

(Example 3)
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanatepropyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 463 parts by mass of N-methylpyrrolidone (NMP) were added. To the mixed solution, 87 parts by mass of aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise with stirring. Thereafter, the mixture was raised to 65 ° C. and reacted for 3 hours while maintaining this temperature. Completion of the reaction was confirmed by disappearance of isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

By the above reaction, a silane compound represented by the following formula was obtained.

Example 4
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanate propyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 455 parts by mass of N-methylpyrrolidone (NMP) were added. To the mixed solution, 95 parts by mass of mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise with stirring. Thereafter, the mixture was raised to 65 ° C. and reacted for 2 hours while maintaining this temperature. Completion of the reaction was confirmed by disappearance of isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

(Example 5)
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts by mass of isocyanate propyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and 445 parts by mass of N-methylpyrrolidone (NMP) were added. To the mixed liquid, 91 parts by mass of ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. Thereafter, the mixture was raised to 65 ° C. and reacted for 2 days while maintaining this temperature. Completion of the reaction was confirmed by disappearance of isocyanate peak using IR.
The solid content concentration of the obtained solution was 30% by mass.

(Comparative Example 1)
Isocyanatepropyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) that did not block isocyanate was used.

(Comparative Example 2)
3-Methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

(Comparative Example 3)
A silane compound was obtained in the same manner as in Example 1 except that 42 parts by mass of methyl ethyl ketone oxime was used instead of 108 parts by mass of ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.).

(Synthesis Example 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen blowing tube and a thermometer was charged with 20 g of methacrylic acid, 40 g of benzyl methacrylate, 15 g of hydroxyethyl methacrylate, 25 g of cyclohexylmaleimide, and 300 g of propylene glycol acetate while blowing nitrogen. Dissolved in. After heating to 80 ° C., 1 g of azobisisobutyronitrile was added, and the mixture was kept at 80 ° C. for 8 hours for polymerization. When the methacrylic acid copolymer was measured by gel permeation chromatography, the weight average molecular weight was 28000, and the solid content acid value was 115.

<Preparation of resist material>
(Examples 6 to 10 and Comparative Examples 4 to 6)
Resist materials of Examples 6 to 10 and Comparative Examples 4 to 6 were prepared using the silane compounds of Examples 1 to 5 and the silane compounds of Comparative Examples 1 to 3, respectively. Specifically, in the container, 50 parts by mass of dipentaerythritol hexaacrylate (DPHA) as a polymerizable compound, 100 parts by mass of the methacrylic acid copolymer produced in Synthesis Example 1 as a binder polymer, and silicone as a surfactant Surfactant FZ-2122 (silicone oil, manufactured by Toray Dow Corning) 0.31 parts by mass, 1-methoxypropyl-2-acetate (PGMAc, manufactured by Daicel Chemical Industries) and cyclohexanone (anone, DOMO CHEMICALS) as a solvent And 10.5 parts by mass of 2-methyl-1- (4-methylthio) phenyl) -2-morpholinopropan-1-one (IRGACURE907, manufactured by BASF) as a polymerization initiator and 8 parts by mass of a silane compound. A resist material was prepared by dissolving in a solvent.

(Example 11)
Instead of 8 parts by mass of the silane compound of Example 1, 3 parts by mass of the silane compound described in Example 1 and 5 of 3-trimethoxysilylpropyl succinic anhydride (X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.) A resist material was prepared in the same manner as in Example 10 except that parts by mass were used.

(Test Example 1)
With respect to Examples 6 to 11 and Comparative Examples 4 to 6, adhesion, stability, and voltage holding ratio (Voltage Holding Ratio: hereinafter abbreviated as “VHR”) were measured. Adhesion, stability, and VHR were measured under the following conditions.

[Board adhesion]
A resist material was applied onto the test glass substrate by spin coating so that the applied film thickness was 1.5 to 2.0 μm, and allowed to stand for 120 seconds. This was pre-baked on a hot plate at 90 ° C. for 120 seconds. The entire surface of the test substrate is exposed with ultraviolet rays. The exposure amount was about 100 mJ / cm ² . Next, it developed for 60 second using the developing solution of 0.1 mass% potassium hydroxide aqueous solution. Furthermore, it was post-baked on a hot plate at 230 ° C. for 18 minutes.

Using a cutter, the surface of the test substrate was cut into grids at 1 mm intervals. A cellophane tape was affixed to this surface and rubbed tightly with a nail, and then the cellophane tape was peeled off at a stretch and the adhesion was observed with a microscope.
In addition, evaluation of adhesiveness was determined as follows.
○: No tape peeling (adhesion rate 100%).
Δ: Tape partially peeled off (adhesion rate 30 to 99%)
X: Most of the tape peeled off (adhesion rate 0 to 29%).

<High temperature and high humidity adhesion>
It was applied to a thickness of 1.5 to 2.0 μm, and allowed to stand for 120 seconds. This was pre-baked on a hot plate at 90 ° C. for 120 seconds. The entire surface of the test substrate was exposed with ultraviolet rays at an exposure amount of 100 mJ / cm ² . Next, development was performed for 60 seconds using a 0.1 mass% aqueous solution of potassium hydroxide. Further, post-baking was performed on a hot plate at 230 ° C. for 18 minutes to prepare a test base. This base was placed in a pressure cooker tester so that the resist-coated surface faced upward, and maintained at 2 atm and 120 ° C. for 30 minutes.

Using a cutter, the surface of the test substrate was cut into grids at 1 mm intervals. A cellophane tape was affixed to this surface and rubbed tightly with a nail, and then the cellophane tape was peeled off at a stretch and the adhesion was observed with a microscope.
In addition, evaluation of high temperature, high humidity adhesiveness was judged as follows.
○: No tape peeling (adhesion rate 100%).
Δ: Tape partially peeled off (adhesion rate 30 to 99%)
×: Most of the tape is peeled off (adhesion rate 0 to 29%)

[Viscosity stability of resist over time]
The viscosity change of the prepared resist solution after aging for 50 days at room temperature was measured.
○: Viscosity increase rate of 5% or less compared to formulation Δ: Viscosity increase rate of 5% to 20% compared to formulation ×: Viscosity increase rate of 20% or more compared to formulation

[Stability of resist adhesion over time]
The prepared resist solution was allowed to elapse for 7 days, 14 days, 21 days, 28 days, and 50 days at room temperature, and then evaluated in the same manner as in the above high temperature and high humidity adhesion test.

[VHR]
On the glass substrate having an ITO film formed on the surface, the resist materials of the above examples and comparative examples were spin-coated so as to have a film thickness of 2 μm, pre-baked at 90 ° C. for 2 minutes, and then irradiated with ultraviolet rays of 100 J / m. ² irradiation, and then post-baked at 230 ° C. for 18 minutes. Next, this coated substrate was bonded to another glass substrate having an ITO film formed on the surface, a liquid crystal cell was prepared by injecting liquid crystal between the substrates, and annealed at 100 ° C. for 1 hour. With respect to the obtained liquid crystal cell, the voltage holding ratio was measured under the conditions of 60 ° C., voltage load time 60 microseconds, voltage 5 V, and low-pass filter 2 MHz.

Table 1 below shows the results of adhesion, stability, and VHR of Examples 6 to 10 and Comparative Examples 4 to 6.

From the above results, it can be seen that the silane compound according to the present invention is excellent in adhesion and stability. On the other hand, in Comparative Examples 4 and 5 using only the conventional silane coupling agent, it can be seen that the adhesion and stability are not balanced. Moreover, it turns out that it is inferior to all of adhesiveness, stability, and VHR in the comparative example 6 whose compound which blocks a silane coupling agent is not a silicon compound represented by General formula (2).

(Test Example 2)
About the said Example and the comparative example, the pattern was created and adhesiveness and chemical-resistance were measured.

<Patterning development adhesion>
A resist material was applied onto the test substrate by spin coating so that the coating film thickness was 3.5 to 4.0 μm, and was allowed to stand for 120 seconds. This was pre-baked on a hot plate at 90 ° C. for 120 seconds. This test substrate was exposed to ultraviolet rays through a 10 μm square dot mask at an exposure amount of 100 mJ / cm ² . Next, development was performed for 60 seconds using a 0.1% by weight aqueous solution of potassium hydroxide to prepare a test substrate having a dot pattern of 10 μm square. The adhesion of the photo spacer formed on the developed substrate was observed with a microscope.
The development adhesion is evaluated as follows.
○: No peeled dot pattern (adhesion rate 100%).
Δ: Partially peeled dot pattern present (adhesion rate 30 to 99%).
×: Most of the peeled dot pattern is present (adhesion rate 0 to 29%).

<Chemical resistance test adhesion>
The test substrate prepared in the same manner as the patterning adhesion evaluation was further post-baked on a hot plate at 230 ° C. for 18 minutes.

The post-baked substrate was treated with an acid and alkali resistance test solution, and the treated substrate was observed with a microscope to observe peeling and the like.
In addition, the chemical resistance test adhesion was evaluated as follows.
○: No peeling dot pattern (adhesion rate 100%).
Δ: Partially peeled off and dot pattern present (adhesion rate of 30 to 99%).
×: Most peeled dot patterns are present (adhesion rate 0 to 29%).

The adhesion and chemical resistance of the dot patterns of the above examples and comparative examples are as shown in Table 2 below.

From Table 2, it can be seen that the adhesion improver according to the present invention is excellent in adhesion and durability even in pattern formation.

From the above Examples and Comparative Examples, the silane compound of the present invention gives adhesion and stability to resins, paints, resist materials, coating agents, etc., when used in combination with resins, paints, resist materials, coating agents, etc. I found out that I can do it. Further, it has been found that the molded product produced by adding the silane compound of the present invention can avoid the occurrence of image sticking even when used in a liquid crystal display element.

Claims

A silicon compound having an isocyanate represented by the following general formula (1);
An adhesion improver comprising a silane compound which is a reaction product with a silicon compound represented by the following general formula (2).

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. Is a substituted or unsubstituted linear or branched alkylene group having 2 to 18 carbon atoms and may contain a divalent or trivalent linking group, and q is an integer of 1 to 3. r is an integer of 1 to 3.)

(Wherein R 4 to R 6 may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. B is a substituted or unsubstituted carbon group having 2 carbon atoms. A linear or branched alkylene group of ˜15 and may contain a divalent linking group, p is an integer of 0 or 1. X is O, NH, NH—CO—NH, S. s is an integer of 1 to 3. t is an integer of 1 to 3. However, when p = 0, s = 1 and t = 1.)
The adhesion improving agent according to claim 1, wherein the silane compound is a compound represented by the following formula (3) or (4).

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and A represents a substituted or unsubstituted straight chain having 2 to 18 carbon atoms. Or a branched alkylene group which may contain a divalent or trivalent linking group, and B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms; X may be O, NH, NH—CO—NH or S. p is an integer of 0 or 1. q is an integer of 1 to 3. r is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3. )
In the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group represented by A, the divalent or trivalent linking group is at least selected from the group consisting of the following formula [A1]. One,
In the linear or branched alkylene group having 2 to 15 carbon atoms having a linking group represented by B, the divalent linking group is at least one selected from the group consisting of the following formula [B1]. The adhesion improving agent according to claim 1 or 2.

[R 7 and R 8 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, —CH═,

(R 9 and R 10 are alkyl groups having 1 to 5 carbon atoms, m3 is an integer of 1 to 5),

(M4 is an integer from 1 to 5),

(R 11 is an alkyl group having 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane having 3 to 6 carbon atoms which may have a substituent. When a divalent group is bonded to either R 7 or R 8 , the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms and having at least two bonds,
The adhesion improver according to claim 1, wherein the silane compound is a silane compound represented by any one of the following formulas (5) to (8).

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and each represents an alkyl group of 1 to 5. m is an integer of 2 to 18.)

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to (It is an integer of 15.)

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to (It is an integer of 15.)

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to (It is an integer of 15.)
The adhesion improver according to any one of claims 1 to 4, further comprising a silane compound represented by the following general formula (9).

[Wherein R 12 to R 14 may be the same or different and each represents hydroxy or an alkoxy group having 1 to 5 carbon atoms; R 15 represents a carboxylic anhydride group or —CHR 16 COOH (where R 16 represents D is a substituted or unsubstituted C2-C10 linear or branched alkylene group, or a substituted or unsubstituted carbon, or a carboxylic anhydride group, a carboxylic acid group or a carboxylic acid ester group. It is an alkylene group having at least one double or straight chain or branched chain having a number of 2 to 10. ]
A resist material comprising the adhesion improver according to any one of claims 1 to 5.
A silane compound represented by the following general formula (3 ′) or (4 ′).

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and each represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and A represents a substituted or unsubstituted straight chain having 2 to 18 carbon atoms. Or a branched alkylene group which may contain a divalent or trivalent linking group, and B is a substituted or unsubstituted linear or branched alkylene group having 2 to 15 carbon atoms; X is O or NH—CO—NH, p is an integer of 0 or 1. q is an integer of 1 to 3. r is 1 S is an integer of 1 to 3. s is an integer of 1 to 3. t is an integer of 1 to 3.)
In the linear or branched alkylene group having 2 to 18 carbon atoms having a linking group represented by A, the divalent or trivalent linking group is at least selected from the group consisting of the following formula [A1]. One,
In the linear or branched alkylene group having 2 to 15 carbon atoms having a linking group represented by B, the divalent linking group is at least one selected from the group consisting of the following formula [B1]. The silane compound according to claim 7.

[R 7 and R 8 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, —CH═,

(R 9 and R 10 are alkyl groups having 1 to 5 carbon atoms, m3 is an integer of 1 to 5),

(M4 is an integer from 1 to 5),

(R 11 is an alkyl group having 1 to 5 carbon atoms) or a monovalent or divalent group represented by a cycloalkane having 3 to 6 carbon atoms which may have a substituent. When a divalent group is bonded to either R 7 or R 8 , the other is a hydrogen atom or a monovalent group. ],

A substituted or unsubstituted cycloalkane having 3 to 6 carbon atoms and having at least two bonds,
The silane compound according to claim 7, wherein the silane compound is represented by the following general formula (10).

In the formula, R 1 to R 3 may be the same or different, and all or at least one is an alkoxy group having 1 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms. 4 to R 6 may be the same or different and are an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, m is an integer of 2 to 18, and n is 2 to And is an integer of 15. X is O or NH—CO—NH.