JP5610925B2 - Alkali-soluble resin containing silicone resin - Google Patents

Description

  The present invention relates to a photosensitive resin that is cured by irradiation with ultraviolet rays or an electron beam and that is alkali-soluble.

  Silicone resins are excellent in electrical properties, adhesiveness, heat resistance, low water absorption, etc., and are used in many fields such as the electronic material field. In particular, epoxy silicone resins having an epoxy group in the molecule are superior in weather resistance and light resistance compared to aromatic epoxy resins such as bisphenol A type diglycidyl ether and phenol novolac type epoxy resin. ) Useful as a sealing material. Specifically, it is possible to reduce deterioration and discoloration of the resin due to light and heat emitted from the LED element. However, these resins do not have a pattern forming ability by alkali development treatment and have limited applications.

  Moreover, as a resin composition useful in the field of electronic materials such as LED encapsulants, for example, Patent Document 1 discloses a resin composition obtained by reacting a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin and a polyvalent carboxylic acid. An alicyclic epoxy resin obtained by epoxidizing an epoxy resin having an epoxy equivalent of 230 to 1000 g / eq and a cyclic olefin, and an epoxy resin composition for sealing using the same are disclosed. Patent Document 2 discloses a silicone compound in which an isocyanuric acid compound having an epoxy group and a vinyl group and a silicone compound are added, and an isocyanuric acid having an epoxy group is introduced into the side chain. Patent Document 3 discloses a resin composition for a color filter protective film using an epoxy compound having a bisphenolfluorene skeleton. However, the compounds exemplified here do not have a pattern forming ability by alkali development.

  On the other hand, Patent Document 4 discloses an alkali-soluble aromatic resin compound for color filters having a polymerizable double bond and a carboxyl group. However, since the compounds exemplified here have an aromatic group, there is a concern about deterioration of the resin due to light or heat emitted from the LED or the like, and discoloration with time.

JP 2003-277473 A JP 2004-099751 A JP2004-69930 Patent No. 3455296

  Therefore, as a result of intensive studies in order to solve the problems in the conventional resin composition as described above, the present inventors have obtained an epoxy silicone compound and a carboxylic acid containing a polymerizable double bond. It was found that an alkali-soluble silicone resin suitable for the formation of a photosensitive resin composition can be obtained by reacting the resulting polyhydric alcohol compound with dicarboxylic acid or its acid monoanhydride. It has been found that this alkali-soluble silicone resin provides a photosensitive resin composition imparted with alkali developability while maintaining the weather resistance, light resistance and heat resistance of the silicone resin.

  Accordingly, an object of the present invention is to provide an alkali-soluble resin containing a silicone resin that is excellent in weather resistance, light resistance, heat resistance, etc. and can be used as a photosensitive resin composition capable of forming a fine pattern. .

（但し、Ｒ₁は炭素数１〜１０の炭化水素基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｘは内部にヘテロ原子を含んでいても良い２価の置換基を示す。Ｙはイソシアヌル環骨格に、重合性二重結合及びカルボキシル基を含んだ基が結合した置換基を示す。Ｚは水素原子、又はイソシアヌル環骨格に、重合性二重結合及びカルボキシル基を含んだ基が結合した置換基を示す。ｍは独立に０〜１００の数を表し、ｎ及びｐはいずれも０である。） That is, the present invention is an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule represented by the following general formula (1).

(Wherein, R ₁ is .R ₂ showing the hydrocarbon group having 1 to 10 carbon atoms is a hydrocarbon group having 1 to 20 carbon atoms, which may contain therein an ether oxygen atom .X inside A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. A substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton m represents a number of 0 to 100, and n and p are both 0.

（但し、Ｒ₃は水素原子又はメチル基を示す。Ｒ₄は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、エステル結合を含んでいても良い。Ｒ₅は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Lは下記一般式（４）で表される置換基を示す。）

（但し、Ｍは２または３価のカルボン酸残基を示し、ｑは１または２である） Preferred embodiments of the present invention are shown below. That is, the Z that put the general formula (1) hydrogen atom, or an isocyanuric ring skeleton, a substituent inclusive group bonded a polymerizable double bond and a carboxyl group, a substituted when Z is not a hydrogen atom The group is preferably the photosensitive resin composition represented by the following general formula (3).

(However, R ₃ represents a hydrogen atom or a methyl group. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom and an ester bond. R ₅ represents a carbon number. 1 to 20 hydrocarbon groups, which may contain an etheric oxygen atom, and L represents a substituent represented by the following general formula (4).

(Wherein M represents a divalent or trivalent carboxylic acid residue, and q is 1 or 2)

  The alkali-soluble resin represented by the general formula (1) of the present invention has high weather resistance, light resistance, and heat resistance as compared with resins used in resin compositions conventionally used in the field of electronic materials. And has alkali developability. That is, a cured product excellent in weather resistance, light resistance, and heat resistance can be obtained, and a fine pattern can be formed. Therefore, the alkali-soluble resin of the present invention is extremely useful as a color filter-related material, a protective layer for semiconductor devices and the like, a sealing material, and an adhesive.

Hereinafter, the alkali-soluble resin of the present invention will be described in detail.
As will be described later, the alkali-soluble resin represented by the general formula (1) of the present invention has a photopolymerizable double bond derived from a polyhydric alcohol compound having a (meth) acryl group, and thus has a radical polymerizable property. In addition to having an acidic group derived from acid monoanhydride, it has alkali solubility.

  The alkali-soluble resin represented by the general formula (1) is obtained by reacting an epoxy group of an epoxy silicone compound with (meth) acrylic acid, and dihydric acid or its acid monoanhydride to the resulting polyhydric alcohol compound having a polymerizable double bond. It is a carboxyl group-containing silicone resin obtained by reacting a product. Since the alkali-soluble resin of the general formula (1) has both a polymerizable double bond and a carboxyl group, it has excellent photocurability, good developability, and patterning characteristics when an alkali-developable photosensitive resin composition is used. give.

（但し、Ｒ₁は炭素数１〜１０の炭化水素基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｘは内部にヘテロ原子を含んでいても良い２価の置換基を示す。Ａはイソシアヌル環骨格に、エポキシ基を含んだ基が結合した置換基を示す。Ｇは水素原子、又はイソシアヌル環骨格に、エポキシ基を含んだ基が結合した置換基を示す。ｍ、ｎ及びｐは独立に０〜１００の数を表す。） The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is a polymerization obtained by reacting the polyfunctional epoxy silicone compound represented by the general formula (5) with a carboxylic acid containing at least one polymerizable double bond. Derived from a polyhydric alcohol compound containing a double bond.

(Wherein, R ₁ is .R ₂ showing the hydrocarbon group having 1 to 10 carbon atoms is a hydrocarbon group having 1 to 20 carbon atoms, which may contain therein an ether oxygen atom .X inside A divalent substituent which may contain a hetero atom, A represents a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group, G represents a hydrogen atom or an isocyanuric ring skeleton, an epoxy group And a substituent containing a group containing m. M, n and p independently represent a number of 0 to 100.)

（但し、Ｒ₁は炭素数１〜１０の炭化水素基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｘは内部にヘテロ原子を含んでいても良い２価の置換基を示す。Ｇは水素原子、又はイソシアヌル環骨格に、エポキシ基を含んだ基が結合した置換基を示す。ｍ及びｐは独立に０〜１００の数を表す。） In the production of the alkali-soluble resin of the present invention, more preferably polymerization obtained by reacting the polyfunctional epoxy silicone compound represented by the general formula (6) with a carboxylic acid containing at least one polymerizable double bond Derived from a polyhydric alcohol compound containing a double bond.

(Wherein, R ₁ is .R ₂ showing the hydrocarbon group having 1 to 10 carbon atoms is a hydrocarbon group having 1 to 20 carbon atoms, which may contain therein an ether oxygen atom .X inside G represents a divalent substituent which may contain a hetero atom, G represents a hydrogen atom or a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group, and m and p are independently 0 to 100. Represents the number of

（但し、Ｒ₆は炭素数１〜１７の炭化水素基又は単結合である。） R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. These hydrocarbon groups include, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, hexyl groups, octyl groups, isooctyl groups, linear hydrocarbon groups such as decyl groups, cyclohexyl groups, etc. An aromatic hydrocarbon group such as an aliphatic cyclic hydrocarbon group and a phenyl group are not limited to these and may be the same or different. A methyl group is preferred. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. Examples of these hydrocarbon groups include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a decylene group, a dodecylene group, or a divalent substituent represented by the following general formula (7). However, it is not limited to these, and they may be the same or different. A propylene group is preferred.

(Wherein, R ₆ is a hydrocarbon group or a single bond 1 to 17 carbon atoms.)

A in the general formula (5) represents a substituent in which a group containing an epoxy group is bonded to an isocyanuric ring skeleton. Advantageously -R ₇ -R ₈ - can be represented by (R ₉ -E) _l. Here, R ₈ is a group composed of an isocyanuric ring skeleton, and R ₇ and R ₉ are preferably a direct bond or a chain hydrocarbon group, but may contain a hetero atom. E is an epoxy group, and l is 1 to 2, preferably 2.

G in the general formula (5) represents a hydrogen atom or a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group. Substituents other than hydrogen atoms, preferably -R ₇ -R ₈ - can be represented by (R ₉ -E) _l. Here, R ₈ is a group composed of an isocyanuric ring skeleton, and R ₇ and R ₉ are preferably a direct bond or a chain hydrocarbon group, but may contain a hetero atom. E is an epoxy group, and l is 1 to 2, preferably 2. A preferred specific example is a substituent represented by the following general formula (8).

X in General formula (5) shows the bivalent substituent which may contain the hetero atom inside. Examples of these substituents include aliphatic hydrocarbon groups such as ethylene group, propylene group, butylene group, hexylene group, decylene group and dodecylene group, and aromatic hydrocarbon groups represented by the following general formula (9). However, it is not limited to these. An ethylene group or a substituent represented by the following general formula (9) is preferable.

（但し、Ｒ₃は水素原子又はメチル基を示し、Ｒ₅は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｍは２価のカルボン酸残基を示す。） For the reaction of such a polyfunctional epoxy silicone compound and a carboxylic acid containing at least one polymerizable double bond, a known method can be used. Performed using (meth) acrylic acid. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. In this case, examples of the carboxylic acid containing at least one polymerizable double bond include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, hydroxyethyl acrylate as shown in the following general formula (10), and methacrylic acid. And monoesters having a polymerizable double bond obtained by a reaction of (meth) acrylate having a hydroxyl group such as hydroxyethyl acid, polyethylene glycol monoacrylate, and polyethylene glycol monomethacrylate with dicarboxylic acid or acid monoanhydride thereof. .

(However, R ₃ represents a hydrogen atom or a methyl group, R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. M is a divalent carboxylic acid residue. Group.)

  Next, the method for producing an alkali-soluble resin of the present invention represented by the general formula (1) by reaction of an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group, and dicarboxylic acid or its acid monoanhydride Will be explained.

  First, a compound having a polymerizable double bond and a hydroxyl group obtained by reaction of the above-described epoxy silicone compound with a carboxylic acid containing at least one polymerizable double bond such as (meth) acrylic acid (hereinafter referred to as epoxy ( A (meth) acrylate compound) and an acid component are reacted to obtain an alkali-soluble resin represented by the general formula (1). There are no particular restrictions on the reaction conditions such as the solvent and catalyst used at this time. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent. Cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone, etc. It may be a ketone solvent or the like. The catalyst used may be a known catalyst such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine. it can. These are described in detail in JP-A-9-325494. Moreover, as an acid component, it is good to use the acid monoanhydride which can react with the hydroxyl group in an epoxy (meth) acrylate compound molecule | numerator. Here, as the acid monoanhydride, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, an acid anhydride of an aromatic dicarboxylic acid, or the like can be used. Among these, examples of the acid anhydride of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelin. Examples thereof include anhydrides such as acid, sebacic acid, suberic acid, and diglycolic acid, and may also be linear hydrocarbon dicarboxylic acid anhydrides substituted with hydrocarbon groups. Examples of acid anhydrides of saturated cyclic hydrocarbon dicarboxylic acids include acid anhydrides such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and hexahydrotrimellitic acid. Further, an acid anhydride of an alicyclic dicarboxylic acid substituted with a saturated hydrocarbon may be used. Examples of the acid anhydride of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid acid anhydride. . Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic anhydride are preferable as the acid monoanhydride, and succinic acid, itaconic acid, tetrahydroacid are more preferable. It is an anhydride of phthalic acid and trimellitic acid.

  The reaction temperature for synthesizing the alkali-soluble resin represented by the general formula (1) by reacting an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group with an acid component is 20 to 140 ° C. The range of is preferable, More preferably, it is 40-130 degreeC. The molar ratio of the acid monoanhydride when synthesizing the alkali-soluble resin represented by the general formula (1) is 10 to 10 with respect to the hydroxyl group in the epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. It should be 100 mol%. The molar ratio of the acid monoanhydride can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1).

  Below, this invention is demonstrated further in detail based on the Example etc. of alkali-soluble resin represented by General formula (1). The scope of the present invention is not limited by these examples. Moreover, evaluation of the resin in the following examples was performed as follows unless otherwise noted.

[Solid content]
1 g of the resin solution (including the reaction product and alkali-soluble resin) obtained in the examples (and comparative examples) was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ ( g)], and the weight [W ₂ (g)] after heating at 160 ° C. for 2 hours, was obtained from the following equation.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Epoxy equivalent]
After dissolving the resin solution in dioxane, add acetic acid solution of tetraethylammonium bromide and titrate with 1 / 10N-perchloric acid solution using potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.). Asked.

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator (trade name COM-1600, manufactured by Hiranuma Seisakusho Co., Ltd.).

[Molecular weight]
This is a value obtained by calculating the weight average molecular weight (Mw) as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Abbreviations used in Examples and Comparative Examples are as follows.
FHPA: Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid content converted acid value 1.28mgKOH / g)
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Example 1]
In a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, 184 g of polydimethylsiloxane (Si-H equivalent 363 g / eq) having Si-H groups at both ends, 250 g of dioxane, and a platinum catalyst supported on carbon powder ( (Platinum concentration 5%) 0.27g was charged and the internal temperature was raised to 90 ° C. Then, 150g of N-allyl-N ', N "-diglycidyl isocyanurate was added over 3 hours. The mixture was heated to 110 ° C. and stirred while refluxing dioxane.The reaction solution was added dropwise to a 0.1N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The catalyst was filtered through Celite, and 320 g of the epoxy silicone resin (ES1) of the general formula (5) was obtained by distilling off the solvent of the filtrate with an evaporator. Directly inside 5) where p and n are both 0 Having a siloxane bond and an isocyanuric ring skeleton and having an epoxy group at the terminal. The epoxy equivalent of the epoxy silicone resin obtained was 317 g / eq, viscosity was 4.5Pa · s (25 ℃).

Next, in a 1000 ml four-necked flask equipped with a reflux tube, 150 g of the above epoxy silicone resin was charged with 34.10 g (0.47 mol) of acrylic acid, 198.87 g of PGMEA, and 0.62 g of TPP, and stirred at 100 to 105 ° C. for 20 hours while heating. And reacted. Further, 53.49 g (0.35 mol) of THPA was charged into the flask and stirred for 6 hours while heating at 120 to 125 ° C. to obtain an alkali-soluble resin (i) -1. The obtained alkali-soluble resin had a solid content of 54.6 wt%, an acid value (converted to a solid content) of 85.3 mg KOH / g, and Mw by GPC analysis of 2540. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1732 cm ⁻¹ (ester bond), 1409 cm ⁻¹ (vinyl group), and 1186 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Example 2]
In a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, 152 g of polydimethylsiloxane (Si-H equivalent 215 g / eq) having both ends Si-H groups, 152 g of dioxane, and a platinum catalyst supported on carbon powder ( (Platinum concentration 5%) 0.36 g was charged, the internal temperature was raised to 90 ° C., and then 200 g of N-allyl-N ′, N ″ -diglycidyl isocyanurate was added over 3 hours. The mixture was heated to 110 ° C. and stirred while refluxing dioxane.The reaction solution was added dropwise to a 0.1N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The catalyst was filtered through celite, and the solvent of the filtrate was distilled off with an evaporator to obtain 324 g of an epoxy silicone resin (ES2) of the general formula (5). Directly inside 5) where p and n are both 0 Having a siloxane bond and an isocyanuric ring skeleton and having an epoxy group at the terminal. The epoxy equivalent of the epoxy silicone resin obtained was 237 g / eq, viscosity was 0.34Pa · s (25 ℃).

Next, in a 1000 ml four-necked flask with a reflux tube, 150 g of the above epoxy silicone resin was charged with 45.61 g (0.63 mol) of acrylic acid, 224.29 g of PGMEA, and 0.83 g of TPP, and stirred at 100 to 105 ° C. for 20 hours while heating. And reacted. Furthermore, 72.22 g (0.47 mol) of THPA was charged into the flask and stirred for 6 hours under heating at 120 to 125 ° C. to obtain an alkali-soluble resin (i) -2. The obtained alkali-soluble resin had a solid content of 54.7 wt%, an acid value (in terms of solid content) of 101.1 mgKOH / g, and Mw by GPC analysis of 1800. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1730 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Comparative Example 1]
412.52g (0.34mol) of FHPA 50% PGMEA solution, 50.02g (0.17mol) of BPDA, 25.87g (0.17mol) of THPA, 52.0g of PGMEA and TPP in a 1000ml four-necked flask with a reflux condenser 0.90 g was added and stirred at 120 to 125 ° C. for 6 hours with heating to obtain Resin (i) -3. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (in terms of solid content) of 103.0 mg KOH / g, and Mw by GPC analysis of 2600. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1407 cm ⁻¹ (vinyl group), and 1181 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

  Next, the reference example and comparative reference example which concern on manufacture of the photosensitive resin composition using the alkali-soluble resin of this invention and its hardened | cured material are shown. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions and cured products thereof in the following Examples and Comparative Examples are as follows.

(i) -1 component: alkali-soluble resin obtained in Example 1 above
(i) -2 component: alkali-soluble resin obtained in Example 2 above
(i) -3 component: alkali-soluble resin obtained in Comparative Example 1 above
(ii) Component: Dipentaerythritol hexaacrylate
(iii) -1 component: photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907)
(iii) -2 component: 4,4′bis (diethylamino) benzophenone (photosensitizer)
(iv) -1 component: Tetramethylbiphenyl type epoxy resin
(iv) -2 component: epoxy silicone resin (ES2) obtained in Example 2
Solvent-1: Propylene glycol monomethyl ether acetate solvent-2: Dipropylene glycol dimethyl ether additive-1: Silane coupling agent (SH-6040 manufactured by Toray Dow Corning)
Additive-2: Surfactant (FC-430 manufactured by Sumitomo 3M)

  The said compounding component was mix | blended in the ratio shown in Table 1, and the photosensitive resin composition of Reference Examples 1-3 and Comparative Reference Example 1 was prepared. In addition, all the numerical values in Table 1 represent parts by weight.

[Alkali developability]
The photosensitive resin composition shown in Table 1 is applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking is 3.8 to 4.2 μm, and prebaked at 80 ° C. for 3 minutes. A coated plate was prepared. Thereafter, the photocuring reaction was carried out by irradiating ultraviolet rays with a high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 32 mJ / cm ² . Next, this exposed coated plate is developed by dip development in a 0.8 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C or in a 0.35 wt% diethanolamine aqueous solution at 23 ° C, and further washed with water, Unexposed areas were removed. Then, the pattern which concerns on Reference Examples 1-3 and the comparative reference example 1 was obtained by performing the heat drying process for 180 minutes at 180 degreeC using a hot air dryer.

  Table 2 shows the results of evaluating developability, development margin, and the like for the patterns made of the photosensitive resin compositions of Reference Examples 1 to 3 and Comparative Reference Example 1 obtained above. These evaluation methods were performed as follows.

Film thickness:
Measurement was performed using a stylus type step shape measuring device (trade name P-10, manufactured by KLA-Tencor Corp.).

Development time:
During alkali development, the time required to dissolve all the unexposed parts of the coating film was recorded. When the pattern could not be seen even when the development time exceeded 300 seconds, it was marked as x.

Taper shape:
Observe the developed pattern using a scanning electron microscope (trade name VE-7800, manufactured by KEYENCE Corporation). If the pattern cross-section maintains a smooth forward taper, ○, reverse taper or peeling When x occurred, it was set as x.

Line shape:
With respect to the 10 μm line after development, the linearity of the pattern portion and the presence or absence of fringe were evaluated with a length measuring microscope (trade name: XD-20, manufactured by Nikon Corporation). Therefore, the case where the linearity was good and the fringe was not generated was evaluated as ○ <good>, and the case where the fringe was generated and the linearity was poor was evaluated as x <defect>. Each item was evaluated as ◎ only when it was very good.

[Transmissivity]
In addition, the photosensitive resin composition shown in Table 1 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 3.8 to 4.2 μm, and at 80 ° C. for 3 minutes. Pre-baked to prepare a coated plate. Thereafter, the photocuring reaction was performed by irradiating ultraviolet rays with a high-pressure mercury lamp having a wavelength of 365 nm and an illuminance of 32 mJ / cm ² . Thereafter, a heat drying treatment was performed at 230 ° C. for 30 minutes using a hot air dryer, and cured films according to Reference Examples 1 to 3 and Comparative Reference Example 1 were obtained. Then, the transmittance of the obtained coated plate was measured using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000, manufactured by Nippon Denshoku Industries Co., Ltd.), and when the transmittance at a wavelength of 380 nm was 90% or more, less than 90% In the case of, it was evaluated as x.

[Mechanical properties]
Further, the photosensitive resin composition shown in Table 1 was applied on an aluminum substrate coated with a 125 mm × 125 mm release agent using a spin coater so that the film thickness after post-baking was 28 to 32 μm. And prebaked at 110 ° C. for 10 minutes to prepare a coated plate. Thereafter, the photocuring reaction was carried out by irradiating ultraviolet rays with a high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 32 mJ / cm ² . Next, this exposed coated plate was developed by dip development in a 0.8 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C., and further washed with water to remove unexposed portions of the coating film. Then, the heat drying process was performed for 90 minutes at 180 degreeC using the hot air dryer. Furthermore, the coated plate after the heat drying treatment was immersed in hot water at 80 ° C., and the coating film was peeled from the aluminum substrate to obtain cured films according to Reference Examples 1 to 3 and Comparative Reference Example 1. The glass transition point of the cured film is measured using a thermomechanical analyzer (EXSTAR 6000 manufactured by SII Co., Ltd.). When the glass transition point is 130 ° C or higher, X. The results are shown in Table 3.

  As is clear from the results of Table 2 and Table 3, the cured products according to Reference Examples 1 to 3 are excellent in each performance. In particular, the cured products of Reference Examples 2 to 3 are equivalent to Comparative Reference Example 1. It is possible to form a cured product that maintains developability and adhesion, and further has high transmittance. That is, it was found that a cured film having weather resistance, light resistance and heat resistance can be provided while maintaining alkali developability.

  The alkali-soluble resin of the present invention forms a pattern having weather resistance, light resistance, and heat resistance by imparting photocurability and alkali developability to a silicone resin having weather resistance, light resistance, and heat resistance. Can do. Therefore, various display elements such as color liquid crystal display devices, color facsimiles, image sensors, protective layers for color filter protective film materials and black matrix forming materials, or organic devices such as organic semiconductors, sealing materials, adhesives Can be suitably used.

Claims (2)

An alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule.

(Wherein, R ₁ is .R ₂ showing the hydrocarbon group having 1 to 10 carbon atoms is a hydrocarbon group of 1 to 20 carbon atoms, which may contain therein an ether oxygen atom .X inside A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. A substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton m represents a number of 0 to 100, and n and p are both 0. Formula (1) to put that Z is an alkali-soluble resin according to claim 1, wherein the substituent when not hydrogen atom is represented by the general formula (3).

(However, R ₃ represents a hydrogen atom or a methyl group. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom and an ester bond. R ₅ represents a carbon number. 1 to 20 hydrocarbon groups, which may contain an etheric oxygen atom, and L represents a substituent represented by the following general formula (4).

(Wherein M represents a divalent or trivalent carboxylic acid residue, and q is 1 or 2)