JP2011207972A - Photosensitive alkali soluble resin containing cyclic silicone resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali soluble resin containing cyclic silicone resin, which gives a photosensitive resin composition excellent in weather resistance, light resistance, heat resistance, etc., and can form a fine pattern.SOLUTION: The photosensitive alkali soluble resin includes a carboxyl group and a polymerizable unsaturated group in one molecule, and is represented by general formula (1) (wherein Rrepresents a 1-10C hydrocarbon group, Rrepresents a 1-20 hydrocarbon group and may have an ethereal oxygen atom therein, X represents a substituent having a polymerizable double bond and an isocyanuric ring skeleton containing a carboxyl group, and n is a number of 3 to 6).

Description

  The present invention relates to a photosensitive resin that is cured by irradiation with ultraviolet rays or an electron beam and that can be patterned by alkali development.

  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, an epoxy silicone resin having an epoxy group in the molecule is 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. LED) 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, none of the compounds exemplified herein has the ability to form a pattern 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 JP 2004-69930 A Japanese Patent No. 3509269

  Therefore, as a result of intensive studies to solve the problems in the conventional resin composition as described above, the present inventors have reacted a polyfunctional epoxy cyclic silicone compound with a carboxylic acid containing a polymerizable double bond. It was found that an alkali-soluble cyclic silicone resin suitable for forming a photosensitive resin composition can be obtained by reacting a polycarboxylic alcohol compound obtained by the reaction with a dicarboxylic acid or an acid monoanhydride thereof. And by using this alkali-soluble cyclic silicone resin, it succeeded in obtaining the photosensitive resin composition which provided alkali developability, maintaining the weather resistance, light resistance, and heat resistance which cyclic silicone resin has.

  Accordingly, an object of the present invention is to provide an alkali-soluble resin containing a cyclic silicone resin, which can provide a photosensitive resin composition that is excellent in weather resistance, light resistance, heat resistance, etc. and can form a fine pattern. There is.

〔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は一般式（２）で示される置換基であり、Ｘ₁及びＸ₂はそれぞれ重合性二重結合を含み、少なくとも一方はカルボキシル基を含む。ｎは３〜６の数を表す。〕

That is, the present invention is a photosensitive alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule.

[However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. X is a substituent represented by the general formula (2), and X ₁ and X ₂ each contain a polymerizable double bond, and at least one of them contains a carboxyl group. n represents the number of 3-6. ]

〔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、又は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、又は水素原子を示す。〕

（但し、Ｍ₁は２価又は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, X in the general formula (1) is the photosensitive alkali-soluble resin, which is preferably a substituent 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 or an ester bond therein. R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms and may contain an etheric oxygen atom inside. L represents a substituent represented by the following general formula (4) or a hydrogen atom. ]

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

  The photosensitive alkali-soluble resin represented by the general formula (1) of the present invention has high weather resistance, light resistance, and heat resistance compared to resins conventionally used in the field of electronic materials and the like, and alkali developability. Have That is, by using the composition containing the photosensitive alkali-soluble resin of the present invention, a cured product having excellent weather resistance, light resistance, and heat resistance can be obtained, and a fine pattern can be formed. Therefore, the composition containing the photosensitive 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 photosensitive resin of the present invention will be described in detail.
As described later, the photosensitive alkali-soluble resin represented by the general formula (1) of the present invention is a carboxyl group of a carboxylic acid containing at least one polymerizable double bond in the epoxy group of the polyfunctional epoxy compound. In addition to having photocurability derived from the polyhydric alcohol compound formed by bonding, the polyhydric alcohol compound contains an acidic group derived from the reaction of acid monoanhydride. Have.

  The photosensitive alkali-soluble resin of the general formula (1) contains at least one polymerizable double bond in an epoxy group of a polyfunctional epoxy cyclic silicone compound (hereinafter sometimes simply referred to as “epoxy cyclic silicone compound”). A dicarboxylic acid or an acid monoanhydride thereof is reacted with the resulting polyhydric alcohol compound having a polymerizable double bond (hereinafter sometimes referred to as “epoxy acrylate cyclic silicone compound”). It is an epoxy acrylate cyclic silicone resin containing a carboxyl group, obtained by reaction. Since the photosensitive 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 when it is used as an alkali-developable photosensitive resin composition. Give properties.

（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。Ｙ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。ｎは３〜６の数を表す。） A method for producing the photosensitive alkali-soluble resin represented by the general formula (1) will be described in detail. First, an epoxy cyclic silicone compound represented by the general formula (5) is reacted with a carboxylic acid containing at least one polymerizable double bond to synthesize an epoxy acrylate cyclic silicone compound.

(However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. Y is an isocyanuric ring. A substituent in which a group containing an epoxy group is bonded to the skeleton is shown, and n represents a number of 3 to 6.

（但し、Ｒ₆は炭素数１〜１７の炭化水素基又は単結合である。） Here, R ₁ in the general formula (5) is a hydrocarbon group having 1 to 10 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples thereof include linear hydrocarbon groups such as isobutyl group, hexyl group, octyl group, isooctyl group and decyl group, alicyclic hydrocarbon groups such as cyclohexyl group, and aromatic hydrocarbon groups such as phenyl group. It is not limited and each may be the same or different. Of these, 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 such a hydrocarbon group 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 (6). However, it is not limited to these, and they may be the same or different. Of these, a propylene group is preferred.

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

Moreover, Y in General formula (5) shows the substituent which the group containing the epoxy group couple | bonded with the isocyanuric ring frame | skeleton, Preferably, it can represent with -R < ₇ >-(R < ₈ > -E) ₂ . Here, R ₇ is a group comprising an isocyanuric ring skeleton, and R ₈ is preferably a direct bond or a chain hydrocarbon group, but may contain an etheric oxygen atom inside. E is an epoxy group. About this preferable Y, the substituent represented by the following general formula (7) can be illustrated as a specific example.

（但し、Ｒ₃は水素原子又はメチル基を示し、Ｒ₉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。Ｍ₂は２価のカルボン酸残基を示す。） For the reaction of such an epoxy cyclic silicone compound with a carboxylic acid containing at least one polymerizable double bond, a known method can be used. For example, for 1 mol of epoxy groups in the cyclic silicone compound, The reaction is carried out by reacting 1 mol of a carboxyl group of a carboxylic acid containing at least one polymerizable double bond. The reaction product obtained by this reaction is an epoxy acrylate cyclic silicone 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, and acrylic acid represented by the following general formula (8). Dicarboxylic acid having a polymerizable double bond obtained by reaction of (meth) acrylate having a hydroxyl group such as hydroxyethyl, hydroxyethyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate and the like with dicarboxylic acid or its acid monoanhydride These monoesters are also included.

(However, R < ₃ > shows a hydrogen atom or a methyl group, R < ₉ > shows a C1-C20 hydrocarbon group, and may contain the etheric oxygen atom inside. M < ₂ > is bivalent carboxylic acid. Indicates a residue.)

  Next, the reaction of the epoxy acrylate cyclic silicone compound having a polymerizable double bond and a hydroxyl group obtained above with a dicarboxylic acid or an acid monoanhydride of the present invention represented by the general formula (1) A method for obtaining a photosensitive alkali-soluble resin will be described.

  That is, the photosensitive alkali-soluble resin represented by the general formula (1) is obtained by reacting the acid component with the hydroxyl group of the epoxy acrylate cyclic silicone compound. At this time, the reaction conditions such as a solvent and a catalyst to be used are not particularly limited. 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 is preferable to use a ketone solvent. 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.

  As the acid component, it is preferable to use an acid monoanhydride capable of reacting with a hydroxyl group in the epoxy acrylate compound molecule, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid. And acid anhydrides of unsaturated dicarboxylic acids 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 unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic anhydride is preferable, and succinic acid, itaconic acid, tetrahydrophthalic acid are more preferable. It may be an acid or an anhydride of trimellitic acid.

  The reaction temperature when synthesizing the photosensitive alkali-soluble resin represented by the general formula (1) by reacting the epoxy acrylate cyclic silicone compound with the acid component is preferably in the range of 20 to 140 ° C, more preferably. 40-130 ° C. The molar ratio of the acid monoanhydride when synthesizing the alkali-soluble resin represented by the general formula (1) is preferably 10 to 100 mol% with respect to the hydroxyl group in the epoxy acrylate cyclic silicone compound. The molar ratio of the acid monoanhydride is determined for the purpose of adjusting the acid value of the photosensitive alkali-soluble resin represented by the general formula (1), and can be arbitrarily changed within the above range.

  Below, this invention is demonstrated further in detail based on the Example of photosensitive alkali-soluble resin represented by General formula (1). The scope of the present invention is not limited by these examples. Moreover, evaluation of resin in the following Examples and Comparative 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 50 wt%, solid content converted acid value 1.28 mgKOH / 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 with a nitrogen inlet tube and a reflux tube, 48 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 480 g of dioxane, and 0.04 g of platinum catalyst supported on carbon powder (platinum concentration 5%) After charging, the internal temperature was raised to 90 ° C., and then 224 g of N-allyl-N ′, N ”-diglycidyl isocyanurate was added over 3 hours. After completion of the addition, the temperature was raised to a temperature at which dioxane began to reflux. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated, and the remaining platinum catalyst was filtered through Celite. The solvent of the liquid was distilled off to obtain 240 g of an epoxy silicone resin (CES1) of the general formula (5), and the resulting epoxy cyclic silicone resin was such that R ₁ in the general formula (5) was a methyl group, n Is 4 and the ring silo The epoxy cyclic silicone resin has an epoxy equivalent of 174 g / eq and a viscosity of 0.5 Pa · s (150 ° C). .

Next, in a 1000 ml four-necked flask equipped with a reflux tube, with respect to 150 g of the above epoxy cyclic silicone resin, 61.97 g (0.86 mol) of acrylic acid, 259.57 g of PGMEA, and 0.57 g of TPP were charged at 100 to 105 ° C. The reaction was stirred for 20 hours under heating. Furthermore, 98.37 g (0.65 mol) of THPA was charged into the flask and stirred for 6 hours while heating at 120 to 125 ° C. to obtain photosensitive alkali-soluble resin (i) -1. The obtained photosensitive alkali-soluble resin had a solid content of 54.9 wt%, an acid value (in terms of solid content) of 121.2 mgKOH / g, and Mw by GPC analysis of 2230. From the IR measurement of the obtained photosensitive alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Example 1]
Platinum catalyst supported on carbon powder with 184 g of polydimethylsiloxane (SI-H equivalent 363 g / eq) with Si-H groups at both ends, 250 g of dioxane, and carbon powder in a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux tube (Platinum concentration 5%) 0.27 g was charged, the internal temperature was raised to 90 ° C., and then 150 g of N-allyl-N ′, N ″ -diglycidyl isocyanurate was added over 3 hours. The temperature was raised to 110 ° C., and the mixture was heated 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 platinum catalyst was filtered through Celite, and the solvent of the filtrate was distilled off with an evaporator to obtain 320 g of an epoxy silicone resin (ES1) of the following general formula (9). R ₁ is a methyl group in the general formula (9) A is 8, has a linear siloxane skeleton and an isocyanuric ring skeleton, and has an epoxy group at the terminal, and the epoxy silicone resin thus obtained has an epoxy equivalent of 317 g / eq and a viscosity of 4.5 Pa · s. (25 ° C).

Next, in a 1000 ml four-necked flask equipped with a reflux tube, with respect to 150 g of the epoxy silicone resin, was charged 34.10 g (0.47 mol) of acrylic acid, 198.87 g of PGMEA, and 0.62 g of TPP and heated at 100 to 105 ° C. The reaction was stirred for 20 hours below. Further, 53.49 g (0.35 mol) of THPA was charged into the flask and stirred for 6 hours under heating at 120 to 125 ° C. to obtain photosensitive alkali-soluble resin (i) -2. The obtained photosensitive 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 photosensitive alkali-soluble resin, peaks were observed at 1732 cm ⁻¹ (ester bond), 1409 cm ⁻¹ (vinyl group), and 1186 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Example 2]
Platinum catalyst supported on carbon powder by 152g of polydimethylsiloxane (SI-H equivalent 215g / eq) with Si-H groups at both ends, 152g of dioxane, and carbon powder in a 1000ml four-necked flask with nitrogen inlet and reflux tube (Platinum concentration: 5%) 0.36 g was charged and 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 temperature was raised to 110 ° C., and the mixture was heated 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 platinum 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 following general formula (9). R ₁ is a methyl group in the general formula (9) A is 4, has a linear siloxane skeleton and an isocyanuric ring skeleton, and has an epoxy group at the terminal, and the epoxy silicone resin thus obtained has an epoxy equivalent of 237 g / eq and a viscosity of 0.34 Pa · s. (75 ° C.).

Next, in a 1000 ml four-necked flask with a reflux tube, 45.61 g (0.63 mol) of acrylic acid, 224.29 g of PGMEA, and 0.83 g of TPP are charged to 150 g of the above epoxy silicone resin and heated at 100 to 105 ° C. The reaction was stirred for 20 hours below. Further, 72.22 g (0.47 mol) of THPA was charged into the flask and stirred for 6 hours while heating at 120 to 125 ° C. to obtain photosensitive alkali-soluble resin (i) -3. The obtained photosensitive 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 an Mw of 1800 by GPC analysis. From the IR measurement of the resulting photosensitive alkali-soluble resin, peaks were observed at 1730 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Example 3]
412.52 g (0.34 mol) of FHPA 50% PGMEA solution, 50.02 g (0.17 mol) of BPDA, 25.87 g (0.17 mol) of THPA, 52.0 g of PGMEA in a 1000 ml four-necked flask with a reflux condenser, and 0.90 g of TPP was charged and stirred at 120 to 125 ° C. for 6 hours with heating to obtain photosensitive alkali-soluble resin (i) -4. 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 photosensitive alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1407 cm ⁻¹ (vinyl group), and 1181 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

  Next, a reference example and a comparative reference example relating to the production of the photosensitive resin composition and its cured product will be specifically described. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions and cured products thereof in the following Reference Examples and Comparative Reference Examples are as follows.

(i) -1 component: photosensitive alkali-soluble resin obtained in Example 1 above
(i) -2 component: photosensitive alkali-soluble resin obtained in Comparative Example 1 above
(i) -3 component: photosensitive alkali-soluble resin obtained in Comparative Example 2 above
(i) -4 component: photosensitive alkali-soluble resin obtained in Comparative Example 3
(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 cyclic silicone resin (CES1) obtained in Example 1
(iv) -3 component: epoxy silicone resin (ES2) obtained in Comparative 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 component was mix | blended in the ratio shown in Table 1, and the photosensitive resin composition of the reference example 1 and the comparative reference examples 1-4 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, UV irradiation with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed with a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction of the photosensitive portion. 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 Example 1 and Comparative Reference Examples 1-4 was obtained by heat-drying for 90 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 Example 1 and Comparative Reference Examples 1 to 4 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 In the case where the cross-sectional shape of the pattern occurred, it was marked 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.

The tackiness of the coating surface:
The tackiness of the coating surface prepared by prebaking at 80 ° C. for 3 minutes was evaluated. The case where there was no tackiness was marked as ◯, the case where there was a slight tackiness, Δ, and the case where there was marked tackiness, ×.

Coating film shrinkage:
The film thickness [thickness: T ₀ (μm)] of the coating film after development and the film thickness [thickness: T ₁ (μm)] after heat drying at 180 ° C. for 90 minutes were determined from the following formula. . When the contraction rate of the coating film was 10% or more, ×, when 5 to 10%, ○, and when it was 5% or less, ◎.
Coating film shrinkage (%) = 100 × (1−T ₁ / T ₀ )

[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, UV curing with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed by a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction. Then, the heat-drying process was performed for 30 minutes at 230 degreeC using the hot air dryer, and the cured film which concerns on the reference example 1 and the comparative reference examples 1-4 was 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, UV irradiation with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed with a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction of the photosensitive portion. 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 off from the aluminum substrate to obtain cured films according to Reference Example 1 and Comparative Reference Examples 1 to 4. Then, the glass transition point of the cured film was measured using a thermomechanical analyzer (EXSTAR 6000 manufactured by SII Co., Ltd.), and when the glass transition point was 160 ° C. or higher, ◎, 145 ° C. to 160 ° C. ◯ in the case, Δ in the case of 130 ° C to 145 ° C, and x in the case of less than 130 ° C. The results are shown in Table 3.

  As is clear from the results of Tables 2 and 3, the cured product according to Reference Example 1 maintains the same developability and adhesion as Comparative Reference Examples 1 to 4, and further has high transmittance and pattern linearity. A cured product having can be formed. In addition, the coating film shrinkage rate can be reduced and the tackiness of the coating film surface can be improved. 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 composition comprising the photosensitive alkali-soluble resin of the present invention is a cyclic silicone resin having weather resistance, light resistance, and heat resistance. By using a resin imparted with photocurability and alkali developability, weather resistance, light resistance Pattern having heat resistance and heat resistance can be formed. Therefore, the composition containing the photosensitive alkali-soluble resin of the present invention includes various display elements such as a color liquid crystal display device, a color facsimile, and an image sensor, a color filter protective film material, a black matrix forming material, or an organic semiconductor. It can use suitably as protective layers, sealing materials, adhesives, etc., such as organic devices.

Claims (2)

A photosensitive alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule.

[However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. X is a substituent represented by the general formula (2), and X ₁ and X ₂ each contain a polymerizable double bond, and at least one of them contains a carboxyl group. n represents the number of 3-6. ]

The photosensitive alkali-soluble resin according to claim 1, wherein X in the general formula (1) is a monovalent substituent 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 or an ester bond therein. R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms and may contain an etheric oxygen atom inside. L represents a substituent represented by the following general formula (4) or a hydrogen atom. ]

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