TW202244135A - Composition for forming film, laminate obtained by applying the composition for forming film, fingerprint authentication sensor including the laminate, and method for forming cured film - Google Patents

Abstract

The present invention provides a composition for forming a film, which has excellent developability, is capable of suppressing curing shrinkage even if the film thickness of a cured film is increased, and is capable of forming a cured film with high hardness. The composition for forming a film of the present invention is characterized by including a siloxane polymer, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, a curing agent, a photoacid generator, a curing catalyst and an organic solvent, the siloxane polymer contains the following silane compound as a constituent monomer: a silane-based compound (A), which contains an amide bond and a carboxylic acid moiety or a carboxylate moiety or the organic groups of the two in the molecule; a silane-based compound (B), which has a free radical polymerizable unsaturated double bond; and a silane-based compound (C), which has an epoxy group in the molecule; the molar ratio [the silane-based compound (A): the silane-based compound (B)] of the silane compound (A) and the silane-based compound (B) is from 1:0.8 to 2.4, the molar ratio [the silane-based compound (C)/total constituent monomers constituting the siloxane polymer] of the silane-based compound (C) relative to the total constituent monomers constituting the siloxane polymer is from 7 to 50.

Description

Film-forming composition, layered product coated with the film-forming composition, fingerprint authentication sensor using the layered product, and method for forming a cured film

The present invention relates to a film-forming composition, a laminate obtained by applying the film-forming composition, a fingerprint authentication sensor using the laminate, and a method for forming a cured film.

In recent years, fingerprint authentication is sometimes used for security protection. Especially in mobile applications such as smart phones, those with such fingerprint authentication functions are widely circulated in the market.

Sensors with this type of fingerprint authentication sometimes use silicide as the bonding pad. For example, Patent Document 1 discloses a junction structure characterized in that an SiO _{2 film is formed on Si, a BPSG film or PSG film is formed on the SiO 2 film} , and a BPSG film or PSG film is formed on the BPSG film or PSG film. There is a SiN film, a Poly-Si film is formed on the SiN film, and an Al-based wire is bonded to the Poly-Si film. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-105291

[Problem to be Solved by the Invention]

The aforementioned bonding pad (corresponding to the Poly-Si film in Patent Document 1) can be formed by photolithography. Therefore, it is required that the film-forming composition for forming a bonding pad has excellent developability.

In addition, in the application of fingerprint authentication, since there may be bonding pads near the surface, from the viewpoint of preventing accidental damage, the cured film is required to have high hardness.

In order to achieve such a high hardness, a method of using a polyfunctional photopolymerizable compound as a film-forming composition for forming a bonding pad, or a method of thermally curing a film-forming composition at a high temperature has been studied, but this method There are also problems such as cracking due to hardening shrinkage.

On the other hand, fingerprint authentication requires excellent light-gathering performance. In order to realize this light-gathering performance, it is necessary to increase the film thickness of the bonding pad (for example, 10 μm or more).

Therefore, a film-forming composition that is excellent in developability even when the film thickness is increased, and capable of suppressing curing shrinkage and forming a cured film with high hardness is desired.

Therefore, an object of the present invention is to provide a film-forming composition that is excellent in developability even when the film thickness of the cured film is increased, and capable of suppressing curing shrinkage and forming a cured film with high hardness. [Technical means to solve the problem]

As a result of diligent research, the inventors of the present invention found that: a photopolymerizable compound containing a siloxane polymer, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, a hardener, a photoacid generator, In the film-forming composition of a curing catalyst and an organic solvent, focus is placed on a siloxane polymer, and as a material constituting the siloxane polymer, the following silane-based compound is contained as a constituent monomer: silane-based compound (A) , which contains an organic group having an amide bond and the following carboxylic acid moiety in the molecule; a silane compound (B), which has a free radical polymerizable unsaturated double bond; and a silane compound (C), which has a molecular There is an epoxy group in it; the blending amount of the above-mentioned silane-based compound (A) and the above-mentioned silane-based compound (B) is set within the specified range, and the above-mentioned silane By setting the compounding amount of the compound (C) within a specified range, even if the film thickness of the cured film is increased, the developability is excellent, and shrinkage on hardening can be suppressed, and a cured film with high hardness can be formed, solving all the above problems. Problem, thus complete the present invention.

That is, the present invention is a film-forming composition characterized by containing a siloxane polymer, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, a curing agent, a photoacid Generating agent, hardening catalyst and organic solvent, the above-mentioned siloxane polymer contains the following silane compound as a constituent monomer: silane compound (A), which contains amide bond and carboxylic acid moiety or carboxylic acid moiety in its molecule The organic group of the ester moiety or both; the silane compound (B), which has a radically polymerizable unsaturated double bond; and the silane compound (C), which has an epoxy group in the molecule; the above silane compound ( The molar ratio of A) to the above-mentioned silane-based compound (B) [the above-mentioned silane-based compound (A): the above-mentioned silane-based compound (B)] is 1:0.8 to 2.4, and the above-mentioned silane-based compound (C) is relatively The molar ratio of all the monomers constituting the oxane polymer [the silane-based compound (C)/the total monomers constituting the siloxane polymer] is 7-50.

In the film-forming composition of the present invention, the above-mentioned siloxane polymer preferably further contains the following silane-based compound as a constituent monomer: a silane-based compound (D) selected from tetraalkoxysilane and bis At least one of the group of (trialkoxysilyl)alkanes; and/or silane compound (E), which is selected from the group consisting of alkyltrialkoxysilane, dialkyldialkoxysilane, cycloalkyl At least one kind selected from the group of trialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane. Moreover, it is preferable that the molar ratio [the said silane type compound (D): the said silane type compound (E)] of the said silane type compound (D) and the said silane type compound (E) is 1:0.1-10. Furthermore, the present invention is also a laminate characterized by having a cured film of the above-mentioned film-forming composition on a base material. In addition, the present invention is also a fingerprint authentication sensor, which is characterized in that it is formed by using the above-mentioned laminated body. Furthermore, the present invention is also a method for forming a cured film, which is characterized by comprising the following steps: a coating step of applying the above-mentioned film-forming composition to a substrate; an exposure step of irradiating the exposed portion with active energy rays to form a cured film and a developing step, using a developing solution to dissolve and remove the coating solution on the unexposed portion. [Effect of Invention]

The present invention can provide a film-forming composition that is excellent in developability even if the film thickness of the cured film is increased, can suppress curing shrinkage, and can form a cured film with high hardness.

The film-forming composition of the present invention is characterized by containing a siloxane polymer, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, a hardener, a photoacid generator, a hardener Catalyst and organic solvent, the above-mentioned siloxane polymer contains the following silane compound as a constituent monomer: silane compound (A), which contains an amide bond and a carboxylic acid moiety or carboxylate moiety or its The organic groups of the two; the silane compound (B), which has a free radical polymerizable unsaturated double bond; and the silane compound (C), which has an epoxy group in the molecule; the above silane compound (A) and the above The molar ratio of the silane-based compound (B) [the above-mentioned silane-based compound (A): the above-mentioned silane-based compound (B)] is 1:0.8 to 2.4, and the above-mentioned silane-based compound (C) is relative to the composition of the above-mentioned siloxane polymer The molar ratio [the above-mentioned silane-based compound (C)/all the constituent monomers constituting the above-mentioned siloxane polymer] of the total constituent monomers is 7-50.

In the film-forming composition of the present invention, by having not only the carboxylic acid moiety or the carboxylate moiety or both in the siloxane polymer, but also having an amide bond of a specific equivalent, even a high film It is thick (10 μm or more) and has good developability. By having a radically polymerizable unsaturated double bond and an epoxy group in a specific equivalent ratio, it can have high hardness even at a high film thickness, and can resist hardening at the same time. The film imparts the effect of inhibiting hardening shrinkage. However, the present invention can also be interpreted without being limited to the above mechanism.

(Silicone polymer) The above-mentioned siloxane polymer contains the following silane compound as a constituent monomer: a silane compound (A), which contains an organic group having an amide bond and a carboxylic acid part or a carboxylate part or both in the molecule; A silane-based compound (B) having a radically polymerizable unsaturated double bond; and a silane-based compound (C) having an epoxy group in a molecule.

＜Silane compound (A)＞ The above-mentioned silane-based compound (A) contains an organic group having an amide bond, a carboxylic acid moiety or a carboxylate moiety or both in the molecule. The so-called organic group having an amide bond and a carboxylic acid moiety or a carboxylate moiety or both in the molecule above means that the silane molecule has a combination of an amide bond and a carboxylic acid moiety (amic acid structure), Either one of an amide bond and a carboxylate moiety (amido ester structure), or both. As the above-mentioned silane compound (A), the hydrolyzable organosilane disclosed in International Publication No. 2011/105368 and its production method can be appropriately selected and used.

As the above-mentioned silane compound (A), it is preferably the reactant obtained by reacting aminopropyltriethoxysilane with succinic anhydride, hexahydrophthalic anhydride or itaconic acid, more preferably aminopropyltriethoxysilane The reaction product of ethoxysilane and succinic anhydride. Specifically, it has a structure represented by the following chemical formula (1).

＜Silane compound (B)＞ The above-mentioned silane compound (B) has a radically polymerizable unsaturated double bond. Examples of the silane compound (B) include: 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc. 3-(meth)acryloxypropyl Silane compounds; allyl silane compounds such as allyl trimethoxysilane and allyl triethoxysilane. Among these, 3-methacryloxypropyltrimethoxysilane is preferred from the viewpoint of high hydrolysis reactivity and crosslink density.

<Molar ratio of siloxane compound (A) to silane compound (B)> The molar ratio of the silane compound (A) to the silane compound (B) in the siloxane polymer [the silane compound (A): the silane compound (B)] is 1:0.8 to 2.4.

If the above-mentioned molar ratio [the above-mentioned silane-based compound (A): the above-mentioned silane-based compound (B)] is less than 1:0.8, the adhesion between the cured film and the substrate or the ITO electrode cannot be sufficiently provided, and the developability (described later) The middle line of the L/S developability test is thicker) decreases, if it exceeds 1:2.4, the solubility of the unhardened film to the developer, especially the solubility to the dilute alkaline developer becomes insufficient (described later Appropriate gaps cannot be formed in the L/S developability test).

The molar ratio of the above-mentioned silane-based compound (A) to the above-mentioned silane-based compound (B) [the above-mentioned silane-based compound (A): the above-mentioned silane-based compound (B)] is preferably 1:1.0-2.0, more preferably 1: 1.5～1.8.

＜Siloxane compound (C)＞ The said siloxane compound (C) has an epoxy group in a molecule|numerator. Examples of the siloxane-based compound (C) include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-epoxypropylmethyldimethoxysilane, Propoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-Epoxycyclohexyl)ethylmethyldimethoxysilane, and 2-(3,4- Epoxycyclohexyl)ethylmethyldiethoxysilane, etc. Among them, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane.

<Molar ratio of siloxane compound (C)> The molar ratio of the siloxane-based compound (C) to all the monomers constituting the siloxane polymer [the silane-based compound (C)/the total monomers constituting the siloxane polymer] is 7~50.

If the molar ratio of the above-mentioned siloxane-based compound (C) is less than 7, curing shrinkage will occur when the above-mentioned film-forming composition is cured, and if the molar ratio of the above-mentioned siloxane-based compound (C) exceeds 50, Then, the solubility of the unhardened film to the developer, especially the solubility to the dilute alkaline developer becomes insufficient (the appropriate gap cannot be formed in the L/S developability test described later).

The siloxane compound (C) preferably has a molar ratio of 15 to 35 with respect to all the monomers constituting the siloxane polymer.

From the viewpoint of providing good adhesion between the cured film and the base material or the ITO electrode, the molar ratio of the above-mentioned silane-based compound (A) to the above-mentioned siloxane-based compound (C) [the above-mentioned silane-based compound (A): The above-mentioned siloxane-based compound (C)] is preferably 1:0.1-1.0, more preferably 1:0.2-0.7, and still more preferably 1:0.3-0.6.

＜Silane compound (D) and silane compound (E)＞ The above-mentioned siloxane polymer preferably further contains the following silane-based compound as a constituent monomer: a silane-based compound (D), which is selected from the group of tetraalkoxysilane and bis(trialkoxysilyl)alkane and/or silane compound (E), which is selected from alkyltrialkoxysilane, dialkyldialkoxysilane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane At least one of the group of alkyl silanes and phenyl trialkoxy silanes.

The said silane type compound (D) is at least 1 sort(s) chosen from the group of tetraalkoxysilane and bis(trialkoxysilyl)alkane.

Examples of the aforementioned tetraalkoxysilane include: tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane Silane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, and methoxytriethoxysilane, etc.

In addition, examples of the bis(trialkoxysilyl)alkane include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl) base) ethane, and 1,2-bis(triethoxysilyl)ethane, etc.

Among them, in terms of versatility, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane are preferred. silane, bis(triethoxysilyl)methane, and 1,2-bis(triethoxysilyl)ethane, more preferably tetramethoxysilane, tetraethoxysilane, and tetraisopropyl Oxysilane.

The above-mentioned silane compound (E) is selected from the group consisting of alkyltrialkoxysilane, dialkyldialkoxysilane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane At least one of the group of silanes. As for the said silane compound (E), it is preferable that it is an alkyltrialkoxysilane as what has a saturated hydrocarbon group, and it is preferable that it is a phenyltrialkoxysilane as what has an unsaturated hydrocarbon group.

Examples of the above-mentioned alkyltrialkoxysilane include: methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltrimethoxysilane, n-butoxysilane, methyl triisobutoxysilane, methyl tri-second butoxysilane, methyl tri-tertiary butoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, Ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltriisobutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane N-propyl silane, n-propyl tri-n-propoxysilane, n-propyl tri-isopropoxy silane, n-propyl tri-n-butoxy silane, n-propyl tri-isobutoxy silane, n-propyl tri-butyl Oxysilane, n-propyltri-tert-butoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane Silane, isopropyltri-n-butoxysilane, isopropyltriisobutoxysilane, isopropyltri-2-butoxysilane, isopropyltri-3-butoxysilane, etc.

Examples of the above-mentioned dialkyldialkoxysilane include: dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane dimethylsilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldisecond-butoxysilane, dimethyldi-tertiary-butoxysilane, diethyldimethylsilane Oxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldiisobutoxysilane Diethylsilane, diethyldi-2-butoxysilane, diethyldi-3-butoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-butoxysilane, di-n-propyldiisobutoxysilane, di-n-propyldi-2-butoxysilane , Di-n-propyl di-tert-butoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiiso Propoxysilane, Diisopropyldi-n-butoxysilane, Diisopropyldiisobutoxysilane, Diisopropyldi-2-butoxysilane, Diisopropyldi-3-butoxysilane , Di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butyl Oxysilane, di-n-butyldiisobutoxysilane, di-n-butyldi-2-butoxysilane, di-n-butyldi-3-butoxysilane, diisobutyldimethoxysilane, Isobutyldiethoxysilane, diisobutyldi-n-propoxysilane, diisobutyldiisopropoxysilane, diisobutyldi-n-butoxysilane, diisobutyldiisobutoxysilane base silane, diisobutyl di-second butoxysilane, diisobutyl di-tertiary butoxysilane, di-second butyldimethoxysilane, di-second butyldiethoxysilane, di- 2nd butyldi-n-propoxysilane, 2nd butyldiisopropoxysilane, 2nd butyldi-n-butoxysilane, 2nd butyldiisobutoxysilane, 2nd Butyl di-2-butoxysilane, di-2-butyl di-3-butoxysilane, di-3-butyldimethoxysilane, di-3-butyldiethoxysilane, di-3-butyl Di-n-propoxysilane, di-tertiary butyldiisopropoxysilane, di-tertiary butyldi-n-butoxysilane, di-tertiary butyldiisobutoxysilane, di-tertiary butyl di- Dibutoxysilane, and di-tertiary butyldi-tertiary butoxysilane, etc.

Examples of the cycloalkyltrialkoxysilane include: cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane Silane, Cyclopentyltri-n-butoxysilane, Cyclopentyltriisobutoxysilane, Cyclopentyltri-2-butoxysilane, Cyclopentyltri-2-butoxysilane, Cyclohexyltrimethoxysilane , cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane, cyclohexyltri-n-propoxysilane Butoxysilane, and cyclohexyl tri-tertiary butoxysilane, etc. Examples of the above-mentioned vinyltrialkoxysilane include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltris- n-butoxysilane, vinyl triisobutoxysilane, vinyl tri-second butoxysilane, vinyl tri-tertiary butoxysilane, etc.

Examples of the above-mentioned phenyltrialkoxysilane include: phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltriisopropoxysilane, N-butoxysilane, phenyl triisobutoxysilane, phenyl tri-second butoxysilane, and phenyl tri-tertiary butoxysilane, etc. Among them, preferably selected from the group of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane At least one kind, more preferably methyltriethoxysilane and phenyltriethoxysilane.

The molar ratio of the silane-based compound (D) to the silane-based compound (E) [the silane-based compound (D): the silane-based compound (E)] is preferably 1:0.1-10. When the molar ratio of the silane-based compound (D) to the silane-based compound (E) is within the above range, both the adhesion of the cured film and the developability of the uncured film can be achieved. The molar ratio of the above-mentioned silane-based compound (D) to the above-mentioned silane-based compound (E) is more preferably 1:1.2-3.

From the viewpoint of the adhesion between the cured film and the substrate or the ITO electrode, and the solubility of the uncured film in the developer solution, the molar ratio of the above-mentioned silane-based compound (A) to the above-mentioned silane-based compound (E) [ The above-mentioned silane-based compound (A): the above-mentioned silane-based compound (E)] is preferably 1:0.1-5.0. The said molar ratio [the said silane compound (A): the said silane compound (E)] is more preferably 1:0.8-3.0, More preferably, it is 1:1.0-2.5.

＜Other silane compounds＞ The above-mentioned siloxane polymer may also contain other silane-based compounds. As other silane-based compounds, silane-based compounds having a mercapto group can be mentioned, for example: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 2-mercaptoethyltrimethoxysilane Mercaptoalkyltrialkoxysilane compounds such as oxysilane.

From the viewpoint of providing good adhesion between the cured film and the substrate or the ITO electrode, the molar ratio of the above-mentioned silane-based compound (A) to the above-mentioned other silane-based compound [the above-mentioned silane-based compound (A): the above-mentioned other silane-based compound Compound] is preferably 1:0.1-1.0, more preferably 1:0.2-0.7, and still more preferably 1:0.3-0.6.

＜Production method of siloxane polymer＞ Next, the manufacturing method of the said siloxane polymer is demonstrated. As a method for producing the above-mentioned siloxane polymer, for example, the following method can be used: after mixing the above-mentioned silane-based compound (A) and the above-mentioned silane-based compound (B) in a suitable container, the above-mentioned silane-based compound (C) . If necessary, the above-mentioned silane-based compound (D), the above-mentioned silane-based compound (E), and the above-mentioned other silane-based compound are mixed, and water, a polymerization catalyst, and an optional reaction solvent are added to make them hydrolyze and condense. After the above-mentioned condensation reaction, use extraction, dehydration, solvent removal and other methods to remove unnecessary by-products other than the above-mentioned siloxane polymer, thereby obtaining the above-mentioned siloxane polymer.

As the quantity of the said water, it is preferable that it is the quantity which makes the quantity of the molecule|numerator of water equal to the quantity of all the hydrolyzable substituents of the silane type compound added in a container. And, since each molecule of the main silane compounds utilized in the present invention has 3 or 4 hydrolyzable substituents, when a large amount of such silane compounds are included, the amount of water can be simply set as the amount of water. The number of molecules is 3 to 4 times the total number of molecules of the silane compound added in the container (the molar ratio is the total amount of the silane compound: water = 1:3 to 4).

As the above-mentioned polymerization catalyst, for example, acid catalysts such as acetic acid and hydrochloric acid; alkaline catalysts such as ammonia, triethylamine, cyclohexylamine and tetramethylammonium hydroxide, can be used. As the amount of the above-mentioned polymerization catalyst, it is preferable that the number of molecules of the polymerization catalyst is 0.05 to 0.2 times that of the total number of molecules of the silane compound added in the container (the molar ratio is the total amount of the silane compound: polymerization catalyst Medium = 1: the amount of the degree of 0.05 ~ 0.2).

As the above-mentioned reaction solvent, lower alcohols such as ethanol, n-propanol and isopropanol, ketone compounds such as acetone and methyl ethyl ketone, esterified products such as ethyl acetate and n-propyl acetate are preferable, and among them, lower alcohols are more preferable. , from the viewpoint of being able to maintain a moderate reaction temperature and being easily distilled off, ethanol and isopropanol are more preferred. The reaction temperature is preferably 60-80° C., and the reaction time is preferably roughly 2-24 hours in order to fully proceed the reaction.

＜Siloxane Polymer＞ The weight average molecular weight (Mw) of the above-mentioned siloxane polymer is preferably 1,000 to 10,000. If the above-mentioned weight average molecular weight (Mw) is less than 1000, the curability of the film-forming composition may decrease, and if the above-mentioned weight-average molecular weight (Mw) exceeds 10,000, the solubility of the film-forming composition may decrease. situation. The weight average molecular weight (Mw) of the said siloxane polymer is more preferably 1,500-8,000, and still more preferably 2,000-4,000.

In addition, as the above-mentioned weight average molecular weight (Mw), the above-mentioned siloxane polymer can be dissolved to prepare a 0.02% by mass solution, which is passed through a filter (manufactured by GL Science Inc., GL chromatodisc (GL chromatodisc), water system 25A , pore diameter 0.2 μm), using a Semi-Micro GPC/SEC analysis system (manufactured by JASCO Corporation) consisting of a size exclusion chromatograph and a refractive index detector, the measurement was carried out under the following conditions. String: KF-603, KF-604 (manufactured by Showa Denko) RI detector: RI-4035 (manufactured by JASCO Corporation) PDA detector: MD-4015 (manufactured by JASCO Corporation) Eluent: THF Flow rate: 1.0ml/min Injection volume: 100 μl

(Photopolymerizable compounds having two or more radically polymerizable unsaturated double bonds) The film-forming composition of the present invention contains a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds.

As the above-mentioned photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, esterification products of hydroxyl-containing compounds having a divalent or higher price and (meth)acrylic acid, such as 1,3-butanediol diol (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate ester, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate ester, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate base) acrylate, tris(2-hydroxyethyl)isocyanuric acid di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, neopentyl Tetraol tri(meth)acrylate, Tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate, Di-trimethylolpropane tetra(meth)acrylate, Neopentylthritol Tetra(meth)acrylate, diperythritol penta(meth)acrylate, dipenteoerythritol hexa(meth)acrylate, and the like.

Among them, from the viewpoint of increasing the crosslinking density and imparting hardness to an excellent cured film, compounds having reactive functional groups with more than three functions are preferred, such as trimethylolpropane tri(meth)acrylate, Glycerin tri(meth)acrylate, Neopentylthritol tri(meth)acrylate, Tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate, Di-trimethylolpropane tetra (Meth) acrylate, neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, and diperythritol hexa(meth)acrylate, more preferably three (2-Hydroxyethyl)isocyanuric acid tri(meth)acrylate, and diperythritol hexa(meth)acrylate.

啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等羰化物；1,3-雙(三氯甲基)-5-(2'-氯苯基)-1,3,5-三

及2-[2-(2-呋喃基)乙烯基]-4,6-雙(三氯甲基)-1,3,5-三

等三鹵甲烷類；2,2'-雙(2-氯苯基)4,5,4',5'-四苯基1,2'-聯咪唑（2,2'-bis(2-chlorophenyl)4,5,4',5'-tetraphenyl 1,2'-biimidazole）等咪唑二聚物；2-異丙基9-氧硫

、2,4-二甲基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

等9-氧硫

系化合物等。 該等光聚合起始劑可單獨使用或組合兩種以上使用。又，亦可與任意光敏劑組合。 (Polymerization initiator) The film-forming composition of the present invention contains a polymerization initiator. As the above-mentioned polymerization initiator, it is preferable to use a photopolymerization initiator that can obtain a sufficient photocuring reaction when forming a cured film by the photolithography method described later. Examples of such photopolymerization initiators include benzophenone, benzoin, benzophenone, camphorquinone, 2,2-dimethoxy-1,2-diphenylethane-1 -ketone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-[4'-(methylthio)phenyl ]-2-

Linyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- Carbonyl compounds such as phenylphosphine oxide; 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-1,3,5-tri

And 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-tri

2,2'-bis(2-chlorophenyl) 4,5,4',5'-tetraphenyl 1,2'-biimidazole (2,2'-bis(2-chlorophenyl )4,5,4',5'-tetraphenyl 1,2'-biimidazole) and other imidazole dimers; 2-isopropyl 9-oxosulfur

, 2,4-Dimethyl 9-oxosulfur

, 2,4-Diethyl 9-oxosulfur

, 2,4-dichloro-9-oxosulfur

9-oxosulfur

Department of compounds, etc. These photopolymerization initiators can be used individually or in combination of 2 or more types. Moreover, it can also combine with arbitrary photosensitizers.

(Organic solvents) The film-forming composition of the present invention contains an organic solvent. As the above-mentioned organic solvent, organic solvents such as alcohols, polyols and derivatives thereof, ketone-based organic solvents, and ester-based organic solvents can be used.

As said alcohols, lower alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and di-butanol, are mentioned.

As said polyols, ethylene glycol, propylene glycol, 1, 2- butanediol, 1, 3- butanediol, diethylene glycol, dipropylene glycol, etc. are mentioned.

Examples of derivatives of the above polyols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, Ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono Phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono Glycol monoethers such as isobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol n-butyl ether, and dipropylene glycol isobutyl ether. Also, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol monomethyl ether acetate, Isopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-isobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether Ester, propylene glycol monoisopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol monoisobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-isopropyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-isobutyl ether acetate, two Propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol mono-n-butyl ether acetate, dipropylene glycol monoisopropyl ether Diol monoether acyl compounds such as butyl ether acetate.

Examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, and cyclohexane Ketones etc.

Examples of the ester-based organic solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, methyl propionate, Ethyl propionate, methyl lactate, ethyl lactate, and n-propyl lactate, etc.

The above organic solvents can be used alone or in combination of two or more. In terms of the solubility and coating suitability of the aforementioned siloxane polymers, polyol derivatives or ester-based organic solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether are more preferred. , propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl ether acetate, n-propyl acetate, and isopropyl acetate.

(hardener) The film-forming composition of the present invention contains a curing agent. Examples of the curing agent include aromatic amine curing agents, acid anhydrides, and phenol novolak resin polysiloxane-based curing agents. Among them, acid anhydrides are preferred, for example, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methylnadic anhydride (methylnadic anhydride), hydrogenated methylnadic anhydride (hydrogenated methylnadic anhydride) anhydride), trialkyl tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenyl succinic anhydride, and benzophenone tetracarboxylic dianhydride, etc.

類、鋶鹽、錪鹽、四級銨鹽類、重氮甲烷化合物、醯亞胺基磺酸鹽化合物、及肟磺酸鹽化合物等。 (Photoacid Generator) The film-forming composition of the present invention contains a photoacid generator. Examples of the above-mentioned photoacid generators include onium salt compounds, trichloromethyl symmetrical tris

Classes, perium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds, etc.

(hardening catalyst) The composition for film formation of this invention contains a hardening catalyst. As said hardening catalyst, the chelate compound of metals, such as aluminum, zirconium, and titanium, is mentioned.

酮類等光敏劑；對苯二酚、對甲氧基苯酚（methoquinone）、受阻胺系、受阻酚系、二第三丁基對苯二酚、4-甲氧基苯酚、丁基羥基甲苯、亞硝胺鹽等聚合抑制劑；無機金屬氧化物、有機微粒子等填充劑等。 (Other materials) The composition for film formation of this invention may contain an additive within the range which does not reduce the effect of this invention. As the above-mentioned additives, for example, carbodiimide-based, isocyanate-based, cross-linking agents having cross-linkable functional groups such as epoxy groups or thiol groups; surfactants such as fluorine-based and polysiloxane-based surfactants; aromatic Hydrocarbons, amino compounds, nitro compounds, quinones,

Photosensitizers such as ketones; hydroquinone, p-methoxyphenol (methoquinone), hindered amine series, hindered phenol series, di-tert-butylhydroquinone, 4-methoxyphenol, butylhydroxytoluene, Polymerization inhibitors such as nitrosamine salts; fillers such as inorganic metal oxides and organic microparticles, etc.

(Content of each material in the film-forming composition) It is preferable to contain 10-50 mass parts of said photopolymerizable compound which has 2 or more radically polymerizable unsaturated double bonds with respect to 100 mass parts of said siloxane polymers. If the content of the above-mentioned photopolymerizable compound having two or more radically polymerizable unsaturated double bonds is less than 10 parts by mass relative to 100 parts by mass of the above-mentioned siloxane polymer, the hardening of the cured film or the substrate or Adhesiveness of the ITO electrode may become insufficient, and if it exceeds 50 parts by mass with respect to 100 parts by mass of the above-mentioned siloxane polymer, the solubility of the unhardened film to the developer may become insufficient.

When the total amount of the above-mentioned siloxane polymer and the above-mentioned polymerizable monomer having two or more radically polymerizable unsaturated double bonds is taken as 100 parts by mass, the above-mentioned polymerization initiator preferably contains 0.5 to 40 parts by mass . If the content of the above-mentioned polymerization initiator is less than 0.5 parts by mass, the photopolymerizability may decrease, and unreacted components may remain in the exposed part of the photolithography method. If it exceeds 40 parts by mass, the film-forming composition may be damaged. Possibility of decreased storage stability. When the total amount of the above-mentioned siloxane polymer and the above-mentioned polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass, it is more preferable that the above-mentioned polymerization initiator contains 1 to 20 parts by mass .

The contents of the curing agent, the photoacid generator, and the curing catalyst are each about 0.1 to 10 parts by mass relative to 100 parts by mass of the siloxane polymer. Moreover, as content of the said additive, it is about 0.1 mass part - 10 mass parts with respect to 100 mass parts of said siloxane polymers, for example.

(Manufacturing method of film-forming composition) As a method for producing the film-forming composition of the present invention, the following method can be used: adding an organic solvent to an appropriate container, for example, while stirring with a high-speed mixer, adding the above-mentioned siloxane polymer, the above-mentioned two The above-mentioned photopolymerizable compound with a radically polymerizable unsaturated double bond, the above-mentioned polymerization initiator, the above-mentioned curing agent, the above-mentioned photoacid generator, the above-mentioned curing catalyst, and other materials as necessary are mixed together. In addition, the manufacturing method of the composition for film formation of this invention is not limited to the said method, The order of adding each material may be arbitrary. Also, if the material in a solid state is soluble in an organic solvent, it may be predissolved before addition, and if it can be directly dispersed in an organic solvent or dispersed with a dispersant, it may be predistributed before addition.

(Physical properties of the film-forming composition) ＜Development＞ The film-forming composition of the present invention is excellent in developability. The above-mentioned developability can be judged by the following L/S developability test, for example.

The film-forming composition was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components became 45%, and the coating conditions were 200 rpm and 60 seconds using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) Then apply it on the glass substrate so that the thickness of the cured film becomes 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, use an ultraviolet parallel exposure device TPE-200SI (manufactured by TECHNOPOST) equipped with a mask engraved with lines and spaces, under the irradiation condition of 100 mJ/cm ² For exposure treatment, immerse a part in 1%Na ₂ CO ₃ /1%Nonal aqueous solution used as a developer for 90 seconds, wash with ion-exchanged water, and heat (post-bake) at 150°C for 30 minutes. After washing with water and drying, a test piece for evaluating the L/S developability of the film-forming composition was produced. The L/S evaluation of the test piece was performed using a film thickness measuring device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor).

In the above-mentioned L/S developability test, when both L (line) and S (space) are 40 μm or less, it can be judged that the developability is excellent.

＜Hardening shrinkage＞ The film-forming composition of the present invention can suppress curing shrinkage during curing. The aforementioned curing shrinkage can be judged by, for example, the following stress measurement test.

The film-forming composition was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components became 45%, and the coating conditions were 200 rpm and 60 seconds using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) Next, apply it on the silicon wafer in such a way that the thickness of the hardened film reaches 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, exposure treatment was performed under the irradiation condition of 100 mJ/cm ² , and a part was immersed in 1% Na ₂ CO ₃ /1% Nonal aqueous solution used as a developer. After soaking for 90 seconds, heat (post-bake) at 150°C for 30 minutes, wash with water, and dry to make a test piece for stress measurement of the hardened film. Stress measurement was performed on this test piece using a thin film stress measurement device FLX-2320 (manufactured by Yamato Material Co., Ltd.).

In the above-mentioned stress measurement test, if the stress is less than 10 mPa, it can be judged that the hardening shrinkage can be sufficiently suppressed.

＜Hardness＞ The film-forming composition of the present invention can form a cured film with high hardness. The hardness of the said cured film can be judged by the following pencil scratch test, for example.

The film-forming composition was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components became 45%, and the coating conditions were 200 rpm and 60 seconds using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) Then apply it on the glass substrate so that the thickness of the cured film becomes 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, exposure treatment was performed under the irradiation condition of 100 mJ/cm ² , and a part was immersed in 1% Na ₂ CO ₃ /1% Nonal aqueous solution used as a developer. After soaking for 90 seconds, heat (post-bake) at 150°C for 30 minutes, wash with water, and dry to make a test piece for measuring the hardness of the hardened film. The evaluation of the pencil scratch test (pencil hardness test) was performed on this test piece in accordance with JIS K 5600-5-4:1999.

In the above-mentioned pencil scratch test, if the hardness is 4H or more, it can be judged to have sufficient hardness.

(How to form hardened film) The method of forming a cured film using the film-forming composition of the present invention preferably includes the following steps: a coating step of applying the above-mentioned film-forming composition to a substrate; an exposure step of irradiating the exposed portion with active energy rays , forming a hardened film; and a developing step, using a developing solution to dissolve and remove the coating solution on the unexposed portion. The method for forming such a cured film is also an aspect of the present invention.

The coating method in the above-mentioned coating step, the active energy ray irradiated to the exposed part and its irradiation method in the above-mentioned exposure step, and the developer for removing the coating solution of the exposed part can be appropriately selected from the known photolithography method. . For example, the film-forming composition can be diluted so that the concentration of non-volatile components reaches 45%, coated with a spin coater, heated (pre-baked) at 80°C for 3 minutes, and aligned using a photomask Exposure machine, under the irradiation condition of 100 mJ/ ^cm2 , the test pattern is exposed, immersed in the developer solution for 1 minute, and then heated (post-baked) at 150°C for 30 minutes to obtain hardening film.

As the conditions for the above-mentioned pre-baking, it is preferable to perform the treatment at 80-100° C. for 1-3 minutes. The irradiation conditions are preferably 20 to 120 mJ/cm ² . As the conditions of the above-mentioned post-baking, it is preferable to process under the conditions of 120-180 degreeC and 30-60 minutes.

In addition, as the above-mentioned substrate, as long as it has light transmittance, it is not limited, and conventionally known ones such as glass substrates and plastic substrates used in touch panels or fingerprint authentication sensors can be used appropriately, and can also be used in A substrate with transparent electrodes formed on its surface. Furthermore, in the case of having a transparent electrode on the surface, it is preferable to form a cured film of the film-forming composition of the present invention on the surface on which the transparent electrode is formed. A laminate characterized by having a cured film of the film-forming composition of the present invention on the aforementioned substrate is also an aspect of the present invention. Moreover, the above-mentioned laminate can be favorably used as a fingerprint authentication sensor, and a fingerprint authentication sensor using the above-mentioned laminate is also an aspect of the present invention. [Example]

Hereinafter, although an Example is disclosed and this invention is demonstrated in detail, this invention is not limited only to these Examples. In addition, unless otherwise specified, "%" means "mass %", and "part" means "mass part".

＜Production of silane compound (A)＞ Put 20.00 g of aminopropyltriethoxysilane into a 200 ml three-necked flask, and while cooling in a water bath, add 9.04 g of succinic anhydride powder, and stir at room temperature for 20 minutes. Thereafter, the obtained crude product is concentrated to obtain the compound represented by the above chemical formula (1). This was used for the synthesis of the siloxane polymer described later.

The following materials were used in the synthesis of the silicone polymer. ＜Silane compound (B)＞ 3-Methacryloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Silane compound (C)＞ 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 3-Glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Silane compound (D)＞ Tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Silane compound (E)＞ Phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Synthesis of siloxane polymers) In a reaction vessel equipped with a stirring device, a reflux cooler, a thermometer and a dropping funnel, dissolve the crude product of the silane compound (A) and the materials in the blending ratios listed in Table 1 in acetone to prepare homogeneous solution. Water and nitric acid were added dropwise thereto, and after mixing for 60 minutes while refluxing, the obtained reaction solution was cooled to room temperature. Thereafter, 20.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, water, and hydrochloric acid, which were reaction by-products, were distilled off under reduced pressure to obtain a hydrolysis-condensation product solution. Then, propylene glycol diethyl ether was added to the hydrolysis-condensation product solution, and the hydrolysis-condensation product solution whose solid content concentration of siloxane polymers 1-13 was 45 mass % was obtained. Furthermore, the weight average molecular weights (Mw) of the above-mentioned siloxane polymers 1 to 13 were measured according to the conditions described in this specification, and all of them were in the range of 1,000 to 10,000.

[Table 1] Silicone polymer 1 2 3 4 5 6 7 8 9 10 11 12 13 Silane compound (A) (mol) Compound of formula (1) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 - 0.7 0.7 0.7 0.7 0.7 Silane compound (B) (mol) 3-Methacryloxypropyltrimethoxysilane 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 - 0.6 0.5 1.8 0.6 Silane compound (C) (mol) 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane 1.2 1.2 1.2 1.2 1.2 - 1.2 - 1.2 - 1.2 1.2 6.0 3-Glycidoxypropyltrimethoxysilane - - - - - 1.2 - 1.2 - - - - - Silane compound (D) (mol) Tetraethoxysilane - 1.0 - 1.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Silane compound (E) (mol) Phenyltrimethoxysilane - - 1.0 1.0 1.0 1.0 4.0 1.0 1.0 1.0 1.0 1.0 1.0 Methyltriethoxysilane - - 2.0 2.0 2.0 2.0 8.0 2.0 2.0 2.0 2.0 2.0 2.0 Silane compound (A): Silane compound (B) 1:0.9 1:0.9 1:0.9 1:0.9 1:0.9 1:0.9 1:0.9 - - 1:0.9 1:0.7 1:2.6 1:0.9 Silane compound (D): Silane compound (E) - - - 1:3 1:1.5 1:3 1:12 1:3 1:3 1:3 1:3 1:3 1:3 Molar ratio of silane compound (C) to all constituent monomers 48.0 34.3 21.8 18.5 16.0 18.5 7.7 20.7 20.3 0.0 18.8 15.6 53.1

(Production of film-forming compositions of Examples 1-9 and Comparative Examples 1-10) In a container equipped with a high-speed stirring device, the hydrolyzed condensate solutions of polysiloxane-based compounds 1 to 13 and the materials in the blending ratios listed in Tables 2 and 3 were added and stirred to prepare a film-forming composition.

The following materials were used in the production of the film-forming compositions of Examples and Comparative Examples. <Photopolymerizable compounds having two or more radically polymerizable unsaturated double bonds> Tris(2-hydroxyethyl)isocyanuric acid triacrylate (referred to as THITA, manufactured by Tokyo Chemical Industry Co., Ltd.) Dineopenylthritol hexaacrylate (referred to as DPHA, manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Hardener＞ Hexahydrophthalic anhydride (manufactured by Nippon Chemical Co., Ltd.) ＜Crosslinking agent＞ Karenz MT PE-1 (thiol-based crosslinking agent, manufactured by SHOWA DENKO Karenz Co., Ltd.) ＜Polymerization initiator＞ Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (referred to as Omnirad819, manufactured by IGM Resins B.V.) ＜Photoacid generator＞ CPI-100P (manufactured by Sanyo Chemical Industry Co., Ltd.) ＜Hardening catalyst＞ K-KAT5218 (aluminum-based hardening catalyst, manufactured by Kusumoto Kasei Co., Ltd.) ZC-700 (zirconium-based hardening catalyst, manufactured by Matsumoto Fine Chemical Co., Ltd.) ＜Other materials＞ BYK-307 (polysiloxane-based surfactant, manufactured by BYK Co., Ltd.)

<L/S Developability Test> The film-forming compositions of Examples and Comparative Examples were diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components reached 45%, and a spin coater (MS-A100 , manufactured by Mikasa Corporation), and coated on the glass substrate under the coating conditions of 200 rpm and 60 seconds so that the thickness of the hardened film reaches 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, use an ultraviolet parallel exposure device TPE-200SI (manufactured by TECHNOPOST) equipped with a mask engraved with lines and spaces, under the irradiation condition of 100 mJ/cm ² For exposure treatment, immerse a part in 1%Na ₂ CO ₃ /1%Nonal aqueous solution used as a developer for 90 seconds, wash with ion-exchanged water, and heat (post-bake) at 150°C for 30 minutes. After washing with water and drying, a test piece for evaluating the L/S developability of the film-forming composition was produced. The L/S evaluation of the test piece was performed using a film thickness measuring device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor). The results are shown in Tables 2 and 3. In addition, in the L/S developability test, when both L (line) and S (space) are 40 micrometers or less, it was judged that it was excellent in developability. The film-forming composition of Comparative Example 5 was evaluated as "-" because it was insoluble in the developer and could not be patterned.

<Stress measurement test> Dilute the film-forming compositions of Examples and Comparative Examples with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components becomes 45%, and use a spin coater (MS-A100, Mikasa Manufactured by the company), and coated on the silicon wafer under the coating conditions of 200 rpm and 60 seconds so that the thickness of the hardened film reaches 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, exposure treatment was performed under the irradiation condition of 100 mJ/cm ² , and a part was immersed in 1% Na ₂ CO ₃ /1% Nonal aqueous solution used as a developer. After soaking for 90 seconds, heat (post-bake) at 150°C for 30 minutes, wash with water, and dry to make a test piece for stress measurement of the hardened film. The test piece was subjected to stress measurement using a thin film stress measurement device FLX-2320 (manufactured by Yamato Material Co., Ltd.), and evaluated according to the following criteria. The results are shown in Tables 2 and 3. (Evaluation criteria) 〇: The stress is less than 10 mPa ×: The stress is more than 10 mPa

<Pencil Hardness Test> Dilute the film-forming compositions of Examples and Comparative Examples with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components becomes 45%, and use a spin coater (MS-A100, Mikasa Co., Ltd.) was coated on the glass substrate under the coating conditions of 200 rpm and 60 seconds so that the thickness of the hardened film reached 10 μm. Next, after heating (pre-baking) at 80°C for 3 minutes, exposure treatment was performed under the irradiation condition of 100 mJ/cm ² , and a part was immersed in 1% Na ₂ CO ₃ /1% Nonal aqueous solution used as a developer. After soaking for 90 seconds, heat (post-bake) at 150°C for 30 minutes, wash with water, and dry to make a test piece for measuring the hardness of the hardened film. The test pieces were evaluated by a pencil scratch test (pencil hardness test) in accordance with JIS K 5600-5-4:1999. The results are shown in Tables 2 and 3. In addition, those whose hardness was 4H or more in the pencil hardness test were judged as having sufficient hardness.

[Table 2] Composition for film formation Example 1 2 3 4 5 6 7 8 9 Silicone polymer (parts by mass, solid content 45% by mass) type 1 1 1 2 3 4 5 6 7 content 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Photopolymerizable compound having two or more radically polymerizable unsaturated double bonds (parts by mass) THITA 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 DPHA 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Hardener (parts by mass) Hexahydrophthalic anhydride 3.0 1.5 1.5 3.0 3.0 3.0 3.0 3.0 3.0 Crosslinking agent (parts by mass) Karenz MT PE-1 - 1.5 1.5 - - - - - - Polymerization initiator (parts by mass) Omnirad819 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Photoacid generator (parts by mass) CPI-100P 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Hardening catalyst (parts by mass) K-KAT5218 2.0 2.0 - 2.0 2.0 2.0 2.0 2.0 2.0 ZC-700 - - 2.0 - - - - - - Other materials (parts by mass) BYK-307 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Evaluation stress test 〇 〇 〇 〇 〇 〇 〇 〇 〇 pencil hardness test 4H 4H 4H 5H 4H 4H 5H 4H 4H L/S developability test L (μm)/S (μm) 40/40 40/40 40/40 40/30 40/40 40/30 40/30 40/40 40/40

[table 3] Composition for film formation comparative example 1 2 3 4 5 6 7 8 9 10 Silicone polymer (parts by mass, solid content 45% by mass) type 1 1 1 1 8 9 10 11 12 13 content 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Photopolymerizable compound having two or more radically polymerizable unsaturated double bonds (parts by mass) THITA 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 DPHA 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Hardener (parts by mass) Hexahydrophthalic anhydride - - 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Crosslinking agent (parts by mass) Karenz MT PE-1 - 3.0 - - - - - - - - Polymerization initiator (parts by mass) Omnirad819 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Photoacid generator (parts by mass) CPI-100P 4.0 4.0 - 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Hardening catalyst (parts by mass) K-KAT5218 2.0 2.0 2.0 - 2.0 2.0 2.0 2.0 2.0 2.0 ZC-700 - - - - - - - - - - Other materials (parts by mass) BYK-307 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Evaluation stress test 〇 〇 〇 〇 〇 〇 x 〇 〇 〇 pencil hardness test 3H 3H 4H 3H 4H 4H 4H 4H 4H 4H L/S developability test L (μm)/S (μm) 60/60 50/60 80/40 80/40 - 150/40 50/40 120/40 40/50 40/100

In Examples 1 to 9 of the film-forming composition of the present invention, it was confirmed that even when the film thickness of the cured film was 10 μm, the developability was excellent, shrinkage on curing was suppressed, and a cured film with high hardness could be formed. In particular, Examples 4 and 5 containing the silane compound (D) and the silane-based compound (E) at a predetermined molar ratio were extremely excellent in developability. [Industrial availability]

The film-forming composition of the present invention increases the film thickness of the cured film, has excellent developability, and can suppress curing shrinkage, and can form a cured film with high hardness, so it can be well used as a light-transmitting coating on touch panels and the like. Insulating film on a permanent substrate.

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Claims (6)

A film-forming composition characterized by containing a siloxane polymer, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, a hardener, a photoacid generator, a hardening trigger media and organic solvents, The above-mentioned siloxane polymer contains the following silane compound as a constituent monomer: a silane compound (A), which contains an organic group having an amide bond and a carboxylic acid part or a carboxylate part or both in the molecule; A silane-based compound (B), which has a radically polymerizable unsaturated double bond; and a silane-based compound (C), which has an epoxy group in its molecule; The molar ratio of the above-mentioned silane-based compound (A) to the above-mentioned silane-based compound (B) [the above-mentioned silane-based compound (A): the above-mentioned silane-based compound (B)] is 1:0.8-2.4, The molar ratio of the above-mentioned silane-based compound (C) to all the constituent monomers constituting the above-mentioned siloxane polymer [the above-mentioned silane-based compound (C)/all the constituent monomers constituting the above-mentioned siloxane polymer] is from 7 to 50. The film-forming composition according to claim 1, wherein the siloxane polymer further contains the following silane-based compound as a constituent monomer: a silane-based compound (D) selected from tetraalkoxysilane and bis( At least one of the group of trialkoxysilyl)alkanes; and/or silane compounds (E) selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkylsilanes, At least one of the group of alkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane. The film-forming composition according to Claim 1 or 2, wherein the molar ratio of the above-mentioned silane-based compound (D) to the above-mentioned silane-based compound (E) [the above-mentioned silane-based compound (D): the above-mentioned silane-based compound (E) ] is 1:0.1-10. A laminate characterized by having a cured film of the film-forming composition according to any one of claims 1 to 3 on a substrate. A fingerprint authentication sensor is made by using the laminate of Claim 4. A method for forming a cured film, characterized by comprising the following steps: a coating step of applying the composition for forming a film according to any one of Claims 1 to 3 on a substrate; an exposure step of irradiating the exposed portion with active energy rays, forming a hardened film; and a developing step, using a developing solution to dissolve and remove the coating solution on the unexposed portion.