KR20140128404A

KR20140128404A - Polysiloxane composition having radical-crosslinkable group

Info

Publication number: KR20140128404A
Application number: KR1020147024580A
Authority: KR
Inventors: 유카 사사키; 도루 가츠마타
Original assignee: 아사히 가세이 이-매터리얼즈 가부시키가이샤
Priority date: 2012-04-20
Filing date: 2013-04-19
Publication date: 2014-11-05
Also published as: KR101566138B1; TW201402700A; WO2013157643A1; JPWO2013157643A1; JP5886420B2; CN104245846A; CN104245846B; TWI491675B

Abstract

The sample was allowed to stand for 24 hours in a dark atmosphere at 24 ° C, atmospheric pressure, and light of a wavelength of 400 nm or less. Thereafter, a peak having a g value of 2.034 to 1.984 was measured with an electron spin resonance (ESR) By weight of a radical-crosslinkable group containing 0.1 x 10 < ^-6 > to 120 x 10 < ^-6 > mol of a radical per g of the solid in the composition.

Description

POLYSILOXANE COMPOSITION HAVING RADICAL-CROSSLINKABLE GROUP [0002]

The present invention relates to an insulating material suitably used for a display device, which is used for forming a surface protective film, an interlayer insulating film, an? Ray shielding film and the like in a semiconductor device and a semiconductor device or the like in which an image sensor or a micromachine or a microactuator is mounted A polysiloxane composition having a radical crosslinkable group suitably used, a cured product obtained by curing the polysiloxane composition or a transparent insulating film.

BACKGROUND ART Polyimide resins having excellent heat resistance, electrical characteristics, and mechanical properties are widely used for insulating materials for electronic parts, surface protective films for semiconductor devices, interlayer insulating films, and alpha ray shielding films. Such a polyimide resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, subjected to soft bake, irradiated (exposed) with an actinic ray through a desired patterning mask, , A cured relief pattern made of a heat resistant polyimide resin can be easily formed (see, for example, Patent Document 1 below).

On the other hand, a polyimide having such excellent properties is not suitable for applications requiring high transparency such as a display device or an optical system material because of the absorption from polyimide rings in the vicinity of 500 nm to 400 nm.

In addition, there is a growing demand for a material capable of performing a heat curing treatment at a lower temperature, mainly for reasons of material or structural design of a component. However, in the case of the conventional polyimide resin precursor composition, the lowering of the curing treatment temperature makes it impossible to complete the heat imidization and the physical properties of the various cured films are lowered, so the lower limit of the curing treatment temperature is around 300 캜.

However, the following Patent Document 2 discloses a photosensitive siloxane-based material capable of being cured at a low temperature.

Patent Document 1: JP-A-6-342211 Patent Document 2: International Publication No. 2010/061744 pamphlet

When the display device or the optical material is formed, the resin forming the pattern is exposed to a high temperature several times and is exposed to a temperature shock due to a change in the surrounding environment after it becomes a final product. Therefore, Is required. However, when the technique disclosed in Patent Document 2 is used, it has been found that there is room for improvement in the crack resistance in the thick film which is required. In addition, in fields requiring high transparency and low temperature curability such as a display device or an optical system material, a photosensitive film forming material satisfying crack resistance in a thick film has not been found yet.

SUMMARY OF THE INVENTION In view of the present situation of the prior art, a problem to be solved by the present invention is to provide a polysiloxane composition having a radical crosslinkable group capable of being cured at a low temperature, which is capable of obtaining a cured product having high transparency and excellent crack resistance due to thermal shock .

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies and experiments to solve the above problems, and as a result, they have unexpectedly discovered that the above problems can be solved by using a polysiloxane composition having a specific radical crosslinkable group, will be. That is, the present invention is as follows.

[1] When measured using an electron spin resonance (ESR) apparatus after being allowed to stand for 24 hours in a dark atmosphere at 24 ° C, atmospheric pressure, and a wavelength of 400 nm or less, g values of 2.034 to 1.984 while having the peak, relative to the total solid content of 100 parts by weight of the composition, 0.1 × 10 ^-6 mol / g ~ 120 × 10 ^-6 polysiloxane composition having a radical crosslinking group comprising a radical of moles / g.

[2] A polysiloxane composition having a radical crosslinkable group according to [1], having the following structure.

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R ¹ and R ² , or R ³ and R ⁴ , They may be combined with each other to form a ring structure.

[3] A polysiloxane composition having a radical crosslinkable group according to [1] or [2], further having an alkali-soluble group.

[4] A polysiloxane composition, further comprising (B) a photo-radical initiator.

(5) a polysiloxane having radical crosslinking group (A) in an amount of 1 part by mass to 99 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition, 0.01 to 15 parts by mass of a photo radical initiator (B) To 2 parts by mass of (C) a nitroxy compound.

[6] The polysiloxane composition according to [5], wherein the (C) nitroxy compound is represented by the following formula:

Wherein R ⁵ represents a monovalent organic group bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl group, or an ether, ester, amide or urethane bond represents, R ⁶ is a divalent or represents a trivalent organic, n ₁ and m ₁ is an integer satisfying _{1≤n 1 + m 1 ≤2, n} 2 and m ₂ is ₂ + 1≤n m ₂ ≤2 N ₃ and m ₃ are integers satisfying ₁ ? N ₃ + m ₃ ? 2, and 1 is an integer of 2 or 3.

[7] The polysiloxane composition according to any one of [1] to [6], wherein the polysiloxane (A) having a radical crosslinkable group is a polysiloxane having a (meth) acryloyl group and / or a styryl group.

[8] The photosensitive resin composition according to any one of [1] to [7] above, which further comprises a compound having a photopolymerizable double bond (D) in an amount of 5 parts by mass to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition Polysiloxane composition.

[9] The polysiloxane composition according to any one of [1] to [8], further comprising 0.01 to 10 parts by mass of (E) an ultraviolet absorber based on 100 parts by mass of the total solid content in the polysiloxane composition.

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising an alkali-soluble resin having an acid value of 10 to 200 mgKOH / g in an amount of 1 to 50 parts by mass per 100 parts by mass of the total solid content in the polysiloxane composition. By weight of the polysiloxane composition.

[11] The polysiloxane composition according to any one of [1] to [10], wherein the polysiloxane (A) having a radical crosslinkable group has a structure represented by the following formula:

Wherein Ph represents a phenyl group.

[12] A cured product obtained by curing the polysiloxane composition according to any one of [1] to [11].

[13] A transparent insulating film obtained by curing the polysiloxane composition according to any one of [1] to [11].

[14] A polysiloxane composition having a radical crosslinkable group, having the following structure.

[15] A polysiloxane composition having the radical crosslinkable group according to [14], further having an alkali-soluble group.

[16] A polysiloxane composition, further comprising (B) a photo-radical initiator.

(B) a photocatalytic initiator, and 0.005 parts by mass (parts by mass) of a polysiloxane having a radical crosslinkable group in an amount of 1 part by mass to 99 parts by mass (A) relative to 100 parts by mass of the total solid content in the polysiloxane composition, To (2) parts by mass of (C) a nitroxy compound.

[18] The polysiloxane composition according to the above [17], wherein the (C) nitroxy compound is represented by the following formula:

[19] The polysiloxane composition according to any one of [14] to [18], wherein the polysiloxane having a radical crosslinkable group (A) is a polysiloxane having a (meth) acryloyl group and / or a styryl group.

[20] The photosensitive resin composition according to any one of [14] to [19], further comprising a compound having a photopolymerizable double bond (D) in an amount of 5 parts by mass to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition Polysiloxane composition.

[21] The polysiloxane composition according to any one of [14] to [20], further comprising 0.01 to 10 parts by mass of (E) an ultraviolet absorber based on 100 parts by mass of the total solid content in the polysiloxane composition.

[22] The photosensitive resin composition according to any one of [14] to [21], further comprising an alkali-soluble resin having an acid value of 10 to 200 mgKOH / g in an amount of 1 to 50 parts by mass based on 100 parts by mass of the total solid content in the polysiloxane composition. By weight of the polysiloxane composition.

[23] The polysiloxane composition according to any one of [14] to [22], wherein the polysiloxane (A) having a radical crosslinkable group has a structure represented by the following formula:

Wherein Ph represents a phenyl group.

[24] A cured product obtained by curing the polysiloxane composition described in any one of [14] to [22] above.

[25] A transparent insulating film obtained by curing the polysiloxane composition according to any one of [14] to [22].

The present invention provides a polysiloxane composition having a radical crosslinkable group capable of obtaining a cured product having high transparency, excellent resistance to cracking due to thermal shock, and low temperature curing.

Fig. 1 shows the result of measurement of electron spin resonance (ESR) of acetone.
Figure 2 shows the ESR measurement results of 4-hydroxy-TEMPO.
3 is a view for explaining a calculation method of g value in ESR.
4 shows the ESR measurement results of the resin compositions of Examples 1 to 8, 12 to 27, and Comparative Example 5.
5 shows the ESR measurement results of the polysiloxane composition of Example 19. Fig.
6 shows the ESR measurement results of the polysiloxane composition of Example 10. Fig.
7 shows the ESR measurement results of the polysiloxane composition of Example 11. Fig.
8 shows the ESR measurement results of the polysiloxane composition of Example 12. Fig.
Fig. 9 shows ESR measurement results of the resin compositions of Comparative Examples 1 to 3. Fig.
10 shows the ESR measurement results of the resin composition of Comparative Example 4. Fig.

Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as "an embodiment") will be described in detail. On the other hand, the present invention is not limited to the embodiment, but can be modified in various ways within the scope of the gist of the invention.

&Lt; Polysiloxane composition having radical crosslinkable group >

The polysiloxane composition having a radical crosslinkable group according to this embodiment specifically includes the following components:

(A) a polysiloxane having a radical crosslinkable group, and

(B) a photo radical initiator,

As desired, other components

. The polysiloxane having a radical crosslinkable group (A) may be composed of a polysiloxane having a radical crosslinkable group and (C) a nitroxy compound, as described below.

Hereinafter, a cured product obtained by curing a polysiloxane composition having a radical crosslinkable group will be described.

However, in the present embodiment, the nitroxy compound is allowed to stand for 24 hours under a condition of shielding light with a wavelength of 24 DEG C, atmospheric pressure, and 400 nm or less in the atmosphere, and then measured using an electron spin resonance (ESR) , It is an example of providing a radical structure having a peak at a g value of 2.034 to 1.984, and the present invention is not intended to be limited to this.

That is, when the polysiloxane (A) and the component (C) are mixed together with the polysiloxane having a radical crosslinkable group (A) described below and the nitroxyl compound as the component (C) A polysiloxane having a radical crosslinkable group is allowed to stand for 24 hours under a condition of shielding light at 24 ° C and atmospheric pressure and 400 nm or less in the atmosphere, When measured using a spin resonance (ESR) apparatus, there is a mixed state of a radical having a peak at a g-value of 2.034 to 1.984 and a radical bonded to the polysiloxane. In the present invention, when such a mixed state is measured by using an electron spin resonance (ESR) apparatus after standing for 24 hours under a condition of shielding light at 24 ° C, atmospheric pressure and a wavelength of 400 nm or less, , and a g value of from 2.034 to 1.984, " a polysiloxane composition having a radical crosslinkable group ". Alternatively, the polysiloxane having a radical crosslinkable group is allowed to stand for 24 hours under a condition of shielding light at a wavelength of 24 DEG C, atmospheric pressure and 400 nm or less in the atmosphere, and then measured using an electron spin resonance (ESR) lt; RTI ID = 0.0 > g < / RTI > value of 2.034 to 1.984. In this case, the polysiloxane group has the predetermined peak. That is, "when measured using an electron spin resonance (ESR) apparatus after being allowed to stand for 24 hours in a dark atmosphere at 24 ° C, atmospheric pressure, and at a wavelength of 400 nm or less, g values of 2.034 to 1.984 Refers to the case where the polysiloxane group having a radical crosslinkable group has the radical generator and the polysiloxane group having a radical crosslinkable group does not have the radical generator. Examples of the polysiloxane having a radical crosslinking group include a nitroxyl compound And a case where the polysiloxane group, the radical, and the polysiloxane group and the radical are combined with each other in a mixed state.

Likewise, " the polysiloxane composition having the radical crosslinkable group further has an alkali-soluble group " means that the polysiloxane itself has an alkali-soluble group and that the composition containing the polysiloxane contains an alkali- And the case where the polysiloxane composition comprises an alkali-soluble group.

In the present embodiment, in order to obtain a cured product excellent in crack resistance due to a thermal shock, the sample is allowed to stand for 24 hours under a condition of shielding light with a wavelength of 24 DEG C, atmospheric pressure, ) with respect to the value of 2.034 g ~ 1.984 g of the solid component 1 is a radical having a peak, as measured using the composition of the unit, 0.1 × 10 ^-6 to it, and more preferably is contained more than 0.15 × 10 ^-6 mol Mole. On the other hand, from the viewpoint of pattern formation is 120 × 10 ^-6 mol or less is preferable, more preferably 60 × 10 ^-6 mol or less.

The total solid content in the polysiloxane composition having a radical crosslinkable group can be measured using, for example, TGA (thermogravimetric analyzer).

The amount of radicals can be measured using ESR (electron spin resonance). Hydroxy TEMPO is prepared as a sample having 1 mole of radical per mole and a calibration curve is prepared so that the amount of radicals in the composition is measured and combined with the solid content measured by TGA to determine the amount of The radical content can be calculated.

In the polysiloxane composition according to the present embodiment, 0.0017 parts by mass of the nitroxyl compound corresponds to a radical amount of 0.1 x 10 ^-6 mol / g, and 0.005 parts by mass of a nitroxyl compound has a radical amount of 0.29 x 10 ^-6 0.009 parts by mass of the nitroxyl compound corresponds to a radical amount of 0.523 占^10-6 mole / g, 1 part by mass of the nitroxyl compound corresponds to a radical amount of 58 占^10-6 mole / g, And 2 parts by mass of the compound corresponded to a radical amount of 116 10 ^-6 mol / g.

&Lt; (A) Polysiloxane having a radical crosslinkable group >

(A) The polysiloxane having a radical crosslinkable group has a group capable of crosslinking by a radical in the polysiloxane, and the hardness of the cured film can be remarkably improved.

The radical crosslinking group may be a group containing a photopolymerizable unsaturated bond (for example, a double bond). The group containing a photopolymerizable unsaturated bond is not particularly limited, and for example, a vinyl group, a styryl group, and a (meth) acryloyl group are preferable from the viewpoint of crosslinkability. The polysiloxane having a radical crosslinking group (A) may contain two or more kinds of these groups. Further, as the polysiloxane (A) having a radical crosslinkable group, those having at least a (meth) acryloyl group and / or a styryl group are more preferable from the viewpoint of the curability.

The molar concentration of the photopolymerizable unsaturated bonding group in the polysiloxane having a radical crosslinking group (A) is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, in view of pattern adhesion, film hardness and crack resistance , More preferably 0.5 mmol / g or more. On the other hand, the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and still more preferably 5.0 mmol / g or less from the viewpoint of reducing the residue upon development.

The content of the photopolymerizable unsaturated bonding group in the polysiloxane having radical crosslinking group (A) can be calculated by measuring the iodine value of the obtained polymer.

(A) the polysiloxane having a radical crosslinkable group preferably contains an alkali-soluble group in one molecule. Examples of the alkali-soluble group include, but are not particularly limited to, a carboxyl group, a dicarboxylic acid anhydride group, or a residue of a dicarboxylic acid anhydride group, which improve the alkali solubility of the polysiloxane and suppress the generation of residue after development .

The content of the carboxyl group, the dicarboxylic acid anhydride group or the dicarboxylic acid anhydride group in the polysiloxane having the radical crosslinking group (A) is not particularly limited as long as the polysiloxane (A) having a radical crosslinkable group has these groups, The acid value of the polysiloxane (A) having a radical crosslinkable group is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoints of reduction of residue after development and crack resistance of the cured film. 20 mgKOH / g or more. On the other hand, from the viewpoint of pattern adhesion, the acid value is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less, and most preferably 180 mgKOH / g or less.

When the polysiloxane composition having a radical crosslinkable group contains polysiloxane having two or more kinds of radical-crosslinkable groups (A), it is preferable that at least one of them contains a carboxyl group, a dicarboxylic acid An anhydride group or a residue of a dicarboxylic acid anhydride group.

In the present specification, the term "acid" refers to the number of milligrams of potassium hydroxide necessary to neutralize the carboxyl group in 1 g of the sample.

An example of a method for measuring the acid value is as follows:

3 g of sample is precisely weighed and dissolved in 20 ml of ethanol. The resulting solution was stirred at room temperature, and further 5 g of purified water was added thereto, followed by further stirring at room temperature for 1 hour. Thereafter, several drops of a methanol solution of phenolphthalein are added as an indicator, neutralization titration is performed with a 1/2 aqueous potassium hydroxide solution, and the acid value is calculated from the amount of the aqueous potassium hydroxide solution used.

In the present embodiment, the polysiloxane having a radical crosslinkable group (A) is preferably obtained by a reaction using at least one silane compound represented by the following formula (I) from the viewpoint of ease of resin design and production method.

^{_{R 7 R 8 a1 Si (R}} 9) 3- a1

(Wherein R ⁷ represents a monovalent organic group having 2 to 20 carbon atoms including a photopolymerizable unsaturated bond group (for example, a double bond group), and R ⁸ each independently represents a straight chain having 1 to 20 carbon atoms, An alkyl group, an aryl group, or an alkylaryl group; R ⁹ independently represents a hydroxyl group, a hydrolyzable leaving group or a halogen atom; and a 1 is an integer of 0 to 2.

In the above formula (I), R ⁹ is preferably selected from the group consisting of a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a phenoxy group, an alkylcarbonyloxy group, chlorine (Cl) or bromine (Br) , More preferably a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group, and more preferably a hydroxyl group, a methoxy group or an ethoxy group from the viewpoint of reactivity.

In the above formula (I), R ⁷ is preferably a monovalent organic group having 2 to 17 carbon atoms and having an unsaturated bond (for example, a double bond), and specific examples thereof include a vinyl group, a styryl group, , A 3- (meth) acryloxypropyl group, a 2- (meth) acryloxyethyl group, and a (meth) acryloxymethyl group. Of these, a styryl group or a 3- (meth) acryloxypropyl group is preferable. In the present specification, (meth) acryl represents an acryl group and a methacryl group.

In another embodiment, the polysiloxane (A) having a radical crosslinkable group may contain an alkali-soluble group, so that at least one silane compound represented by the above formula (I) and at least one silane compound represented by the following formula It is preferable from the viewpoint of easiness of the resin designing and production method that it is obtained by the reaction using one kind of silane compound.

^{_{R 10 R 11 a2 Si (R}} 9) 3- a2

(Wherein R ⁹ is as defined in the above formula (I), R ¹⁰ represents an alkali-soluble group, and R ¹¹ each independently represents a linear or branched organic group having 1 to 20 carbon atoms , An aryl group or an alkylaryl group, and a2 is an integer of 0 to 2.

In the above formula (II), R ¹⁰ is not particularly limited as long as it has a carboxyl group, a dicarboxylic acid anhydride group or a dicarboxylic acid anhydride group residue. Specifically, R ¹⁰ is a group represented by the following formula (II-1) Is preferably selected from the group consisting of an organic group of the following formula (1).

Wherein Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms, Ry and Rz are each independently selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, and hydrogen One or both of Ry and Rz is hydrogen, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms, Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms, , And Rt is a linear, branched or cyclic divalent organic group having 1 to 18 carbon atoms and Ru and Rv each independently represent a divalent organic group having 1 to 20 carbon atoms Branched or cyclic monovalent organic group or a monovalent organic group represented by the following formula (II-2).

Wherein Rw is a linear, branched or cyclic divalent organic group having 1 to 16 carbon atoms and Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms or a linear, And Rc is a group represented by the following formula (II-3) or a hydrogen atom.

Wherein Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms.

In the formula (II), preferred examples of the organic group contained in R ¹⁰ include a succinic anhydride group (R ¹⁰ -1), a cyclohexanedicarboxylic acid anhydride group (R ¹⁰ -2), 4-methylcyclohexanedicarboxylic acid dicarboxylic acid anhydride group (R ¹⁰ -3), 5- methyl-cyclohexane dicarboxylic acid anhydride group (R ¹⁰ -4), bicyclo heptane dicarboxylic acid anhydride group (R ¹⁰ -5), 7- oxa -bicyclo-heptane dicarboxylic acid anhydride group (R ¹⁰ -6), acid anhydride group (R ¹⁰ -7), amber acid or half-ester group (R ¹⁰ -8), cyclohexane dicarboxylic acid or half - ester groups (R ¹⁰ -9), 4- methyl-cyclohexane dicarboxylic acid or half-ester group (R ¹⁰ -10), 5- methyl-cyclohexane dicarboxylic acid or half-ester group ( R ¹⁰ -11), bicyclo heptane dicarboxylic acid or half-ester group (R ¹⁰ -12), 7- oxa-bicyclo heptane dicarboxylic acid or half-ester group (R ¹⁰ -13), Phthalic acid group or its half An ester group (R ¹⁰ -14), a group having an amide bond (R ¹⁰ -15) by reacting an amino group with a dicarboxylic acid anhydride, a group having an isocyanurate skeleton (R ¹⁰ -16) . R ¹⁰ may contain these groups either individually or in combination of two or more.

In the above formula (II-1), Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms. Among them, Rx is preferably a hydrocarbon group from the viewpoint of ease of synthesis. Examples of the hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a n-pentylene group, , tert-pentylene group. These groups may contain a double bond and / or a triple bond, and may be used alone or in combination of two or more. Among them, the propylene group is most preferable.

In the above formula (II-1), the group (R ¹⁰ -15) having an amide bond is a carboxyl group-containing group obtained by the reaction of an amino group and a dicarboxylic acid anhydride. Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms. Examples of the dicarboxylic acid anhydride represented by the above formula (II-1) include anhydrous succinic acid, cyclohexanedicarboxylic acid anhydride, 4-methyl-cyclohexanedicarboxylic acid anhydride, 5-methylcyclohexane Dicarboxylic acid anhydride, dicarboxylic anhydride, bicycloheptanedicarboxylic acid anhydride, 7-oxabicycloheptanedicarboxylic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinic anhydride, and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

In the above formula (II-1), the group (R ¹⁰ -16) having an isocyanurate skeleton is a ring-opening reaction of glycidyl from the isocyanurate skeleton having a glycidyl group by reaction with a carboxyl group or a hydroxyl group Is a group containing a carboxyl group obtained by reacting a generated hydroxyl group with a dicarboxylic acid anhydride.

In formula (II), the most preferable group as R ¹⁰ is a propyl succinic anhydride group (R ¹⁰ -1), a propyl succinic acid group or a half-methyl ester group thereof, or a half-ethyl ester group thereof (R ¹⁰ -8) .

In another embodiment, the polysiloxane (A) having a radical crosslinkable group may further contain at least one silane compound represented by the formula (I) and at least one silane compound represented by the formula (II) Is obtained by a reaction using at least one silane compound represented by the general formula (III), from the viewpoint of easiness of the resin design and production method.

R ¹² _a3 Si (R ⁹ ) _4- _a3

(Wherein R ⁹ is as defined in the above formula (I), R ¹² is a linear or branched organic group having 1 to 20 carbon atoms which may have a substituent, an aryl group, an alkylaryl group And a3 is an integer of 0 to 3.}

Specific examples of the silane compound represented by the above formula (I) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) (Meth) acryloxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (2-propenylphenyl) triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p- (2-propenylphenyl) Methoxysilane and the like.

Among the alkoxysilane compounds containing a carboxyl group, a dicarboxylic acid anhydride group or a half-ester group of a dicarboxylic acid anhydride group as the silane compound represented by the formula (II), the most preferable compound is (3-trimethoxysilylpropyl) succinic acid, (3-triethoxysilylpropyl) succinic acid, (3-trimethoxysilylpropyl) succinic anhydride, ) Half-methyl esters of (3-triethoxysilylpropyl) succinic acid, half-ethyl esters of (3-trimethoxysilylpropyl) succinic acid and (3-triethoxysilylpropyl) succinic acid Lt; / RTI >

In the specific examples of the silane compound represented by the above formula (III), examples of the compound having a polymerizable cyclic ether linking group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triene, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) methyldiethoxysilane.

Specific examples of the silane compound represented by the above formula (III) other than the compound having a polymerizable cyclic ether linking group include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, But are not limited to, methoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, Phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Octadecyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane , N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane Methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, tri-i-propylchlorosilane, and the like can be used. . These may be used alone or in combination of two or more.

(A) a polysiloxane having a radical crosslinkable group can be synthesized by any method. For example, the silane compound represented by the formula (I), the silane compound represented by the formula (II) and the silane compound represented by the formula Is obtained by hydrolyzing a silane compound to be added with water and a catalyst and then subjecting the obtained hydrolyzate to condensation in the presence or absence of a solvent.

The hydrolysis reaction is carried out by adding an acid catalyst and water to the silane compound in the solvent over a period of 1 minute to 180 minutes. From the viewpoint of the reactivity of the hydrolysis, the temperature of the step of obtaining the hydrolyzate is preferably 10 ° C or higher, more preferably 20 ° C or higher, and from the viewpoint of protection of the functional group, Preferably 120 DEG C or less. The reaction time of the step of obtaining the hydrolyzate is preferably 0.1 hour or more, more preferably 0.5 hour or more from the viewpoint of reactivity of hydrolysis, and 10 hours or less from the viewpoint of protection of the functional group, It is less than 5 hours.

The hydrolysis reaction is preferably carried out in the presence of an acidic catalyst. The acidic catalyst is preferably an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid. The preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of reactivity of hydrolysis with respect to all the silane compounds used in the hydrolysis reaction, and 10 mol% or less from the viewpoint of protection of functional groups.

It is preferable that the silanol compound is obtained by the hydrolysis reaction of the silane compound and then the condensation reaction is carried out by heating the reaction solution at 50 캜 or higher and at the boiling point or lower of the solvent used for 1 hour to 100 hours. Further, in order to increase the polymerization degree of the polysiloxane (A) having a radical crosslinkable group, reheating and / or reduced pressure and / or addition of a basic catalyst may be carried out.

The solvent used for the hydrolysis reaction of the silane compound and the condensation reaction of the hydrolyzate is not particularly limited and can be appropriately selected in consideration of stability, wettability, volatility, and the like of the resin composition. In addition, these reactions may be carried out by combining two or more kinds of solvents or by using no solvent.

Specific examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol and diacetone alcohol, Ethers such as glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether, methyl ethyl ketone, Propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, and butyl lactate, ketones such as γ-butyrolactone, methyl ethyl ketone, methyl ethyl ketone, Lactone, N-methyl-2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, .

When a solvent is produced by a hydrolysis reaction, hydrolysis can also be carried out with no solvent. After completion of the hydrolysis reaction, it is also preferable to further adjust the concentration of the resin composition by adding a solvent. Depending on the use of the resin composition, an appropriate amount of the produced alcohol or the like may be distilled off under heating and / or reduced pressure after the hydrolysis, and then a suitable solvent may be added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the total silane compound.

The water used in the hydrolysis reaction is preferably ion-exchange water. The amount of water may be arbitrarily selected, and it is preferably in the range of 1.0 mol to 4.0 mol based on 1 mol of the silane compound used in the hydrolysis reaction.

In the present embodiment, in addition to the reaction described above, (A) the method for producing a polysiloxane having a radical crosslinkable group, water is generated by dehydration condensation of silanol among the silanol groups, , And chlorosilane can be reacted without the addition of water and catalyst.

Silanol (residual silanol), which is present in the polysiloxane having radical crosslinking group (A) and not involved in condensation, is preferably used in view of reduction of shrinkage due to condensation at the time of bake, reduction of degassing of water and alcohol caused by condensation , It is preferable that the amount is small, and it is preferable that the amount is substantially eliminated.

The polysiloxane having a radical crosslinking group (A) preferably has no or little residual silanol. For example, the silanol compound represented by the formula (I) and the silane compound represented by the formula (II) And a silane diol compound represented by the following formula (IV), at least in the presence of a catalyst, or, preferably, without aggressively adding water.

R ¹³ ₂ Si (OH) ₂

Wherein R ¹³ is an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms, They may be the same or different and may be interconnected through a covalent bond.

In the above formula (IV), examples of R ¹³ include phenyl, tolyl, xylyl, trimethylphenyl, naphthyl, methyl, ethyl, cyclopentyl and cyclohexyl groups.

Specific examples of the silane diol compound represented by the formula (IV) include diphenylsilanediol, di-p-toluylsilanediol, dicylsilylsilanediol, ditrimethylphenylsilanediol, di- Naphthylsilanediol, dicyclopentylsilanediol, and cyclohexylmethylsilanediol. From the viewpoint of copolymerization and heat resistance, diphenylsilanediol, dicyclopentylsilanediol, and cyclohexylmethylsilanediol are particularly preferable.

From the viewpoint of the reactivity of the condensation, the temperature for the condensation without actively adding water is preferably 40 ° C or higher, more preferably 50 ° C or higher, and from the viewpoint of protection of the functional group, More preferably 130 DEG C or less.

From the viewpoint of reactivity of the condensation, the time for the condensation without actively adding water is preferably 0.5 hour or more, more preferably 1 hour or more, and preferably 48 hours or less from the viewpoint of protection of functional groups And more preferably 30 hours or less.

In the reaction of condensation without actively adding water, a catalyst is used and water is not actively added. As the catalyst, a basic catalyst or an acidic catalyst may be used.

As the basic catalyst, trivalent or tetravalent metal alkoxides can be used. Specifically, examples of the basic catalyst include trialkylaluminum compounds such as trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, Butoxy aluminum, tri-tert-butoxy aluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-isopropoxyboron, tri- Tri-tert-butoxyborane, tetraethoxy silane, tetraethoxy silane, tetra-n-propoxy silane, tetra-iso-propoxy silane, tetra butoxy silane, tetra-tert-butoxysilane, tetra-tert-butoxy silane, tetramethoxy germanium, tetraethoxy germanium, tetra-n-propoxy germanium, tetra- iso-propoxy germanium, tetra-n-butoxy germanium, tetra-iso-butoxy germanium, tetra- N-propoxytitanium, tetra-n-butoxytitanium, tetra-iso-propyltriethoxysilane, tetrabutyltriethoxysilane, tetrabutyltriethoxysilane, Butoxy titanium, tetra-tert-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetra-iso-propoxy zirconium, tetra- Ethoxyzirconium, tetra-iso-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium and the like.

Further, a hydroxide of an alkali metal or a hydroxide of an alkaline earth metal such as barium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide, calcium hydroxide and magnesium hydroxide may be used as a basic catalyst. NH ₄ F (ammonium fluoride) may also be used as the basic catalyst. Among them, barium hydroxide, sodium hydroxide, strontium hydroxide, tetra-tert-butoxy titanium and tetra-iso-propoxy titanium are preferable. In order to achieve a rapid and uniform polymerization reaction, it is preferable that the basic catalyst is in a liquid phase in the reaction temperature range.

The preferred content of these basic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to the total silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.

As the acid catalyst, an organic acid catalyst which does not contain water can be used. Specific examples of the acidic catalyst include acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid or its half- Succinic acid or its half-ester.

The preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to the total silane compounds, and 10 mol% or less from the viewpoint of protection of functional groups.

In the synthesis of the (A) polysiloxane having a radical crosslinkable group, a polymerization inhibitor may be added during the synthesis from the viewpoint of protection of the crosslinking group.

In addition, in the present embodiment, the polysiloxane (A) having a radical crosslinkable group is also preferable from the viewpoint of heat resistance, having the following structure. The proportion of the silicon atom of the polysiloxane having a radical crosslinking group (A) having the following structure is preferably from 10 mol% to 80 mol%, more preferably from 30 mol% to 70 mol%, still more preferably from 40 mol% mol% to 60 mol%.

Wherein Ph represents a phenyl group.

In the present embodiment, the content of the polysiloxane (A) having a radical crosslinkable group is not particularly limited and may be arbitrarily selected depending on the desired film thickness or application. From the viewpoint of heat resistance and transparency, the total content of solids in the photosensitive resin composition More preferably not less than 10 parts by mass, more preferably not less than 15 parts by mass, and not more than 99 parts by mass from the viewpoint of crack resistance, and more preferably not less than 10 parts by mass Is 90 parts by mass or less, and more preferably 85 parts by mass or less.

&Lt; (B) Photo radical (polymerization) initiator >

It is important that (B) the photo-radical initiator is added to the polysiloxane composition in order to impart the ability to form a photosensitive pattern to the polysiloxane composition.

Examples of the photoradical initiator (B) include the following photoradical initiators (1) to (10):

(1) Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone

(2) acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane- 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by BASF), 2-methyl-1- [4- (methylthio) phenyl] (IRGACURE 907, manufactured by BASF Corporation) and 2-hydroxy-1- {4- [4- (2- hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan- IRGACURE127), methyl phenylglyoxylate

(3) Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone

(4) Benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl- beta -methoxyethyl acetal

(5) benzoin derivatives such as benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCURE 1173,

(6) oxime-based compounds such as 1-phenyl-1,2-butanedione -2- (O-methoxycarbonyl) oxime, 1-phenyl- 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1, 2- (O-benzoyl) oxime, 1, 2-octanedione, 1-phenyl-3-ethoxypropanetrion- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-2-yl) 3-yl] -, 1- (O-acetyloxime) (IRGACURE OXE02, manufactured by BASF)

(7)? -Hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-

(8) α-aminoalkylphenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369, (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (IRGACURE 379,

(9) phosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819 manufactured by BASF), bis (2,6-dimethoxybenzoyl) 4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin TPO, BASF)

(10) titanocene compounds such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- (IRGACURE784, manufactured by BASF)

The above-mentioned photo radical initiators (1) to (10) may be used alone or in combination of two or more.

Among the photocatalytic initiators of (1) to (10), benzoin derivatives or (9) phosphine oxide-based compounds are more preferable from the viewpoint of improving photosensitivity and transparency.

The content of the photocatalytic initiator (B) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, from the viewpoint of obtaining sufficient sensitivity for 100 parts by mass of the total solid content in the polysiloxane composition, It is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of sufficiently curing the bottom portion of the resin layer.

&Lt; (C) Nitroxy compound >

(C) a nitroxy compound is a compound containing a structure represented by the following formula (V). R ¹ , R ² , R ³ and R ⁴ are preferably monovalent organic groups having 1 to 10 carbon atoms. The polysiloxane composition of the present embodiment is excellent in crack resistance after curing in a nitrogen atmosphere by including (C) a nitroxy compound.

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R ¹ and R ² , or R ³ and R ^4, Thereby forming a ring structure.

In the above formula (V), R ¹ , R ² , R ³ and R ⁴ may each independently be an alkyl group or an alkyl group substituted with a hetero atom. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or the like, and the hetero atom is preferably a halogen, oxygen, sulfur, nitrogen or the like.

Examples of the nitroxide compound (C) used in the present embodiment include di-tert-butyl nitroxide, di-1,1-dimethylpropyl nitrite, di-1,2-dimethylpropyl nitrite, di -2,2-dimethylpropylnitroxide and compounds represented by the following formula (VI), (VII) or (VIII) are preferable. Among them, a compound represented by the following formula (VI), (VII) or (VIII) is more preferable from the viewpoint of crack resistance after curing in a nitrogen atmosphere.

Specific examples of the compound represented by the above formula (VI) include the following compounds.

Wherein R ²⁰ each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic group or an alicyclic group, and R ²⁰ may have other substituents.

Specific examples of the compound represented by the above formula (VII) include the following compounds.

Specific examples of the compound represented by the above formula (VIII) include the following compounds.

As the more preferable (C) nitroxy compound, from the viewpoint of crack resistance, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1 Oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-acrylate-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- ( 2-chloroacetamide) -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl benzoate 4-isothiocyanato-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2-iodoacetamide) -2,2,6,6-tetra Methylpiperidine 1-oxyl free radical, and 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical. (C) a nitroxy compound may be used alone or in combination of two or more.

The content of the nitrosoxy compound (C) in the polysiloxane composition is preferably 0.005 part by mass or more based on 100 parts by mass of the total solid content in the polysiloxane composition More preferably not less than 0.009 parts by mass, and not more than 2 parts by mass, and more preferably not more than 1 part by mass, from the viewpoint of transparency.

&Lt; (D) Compound having photopolymerizable double bond >

In the present embodiment, the polysiloxane composition preferably contains (D) a compound having a photopolymerizable double bond from the viewpoint of crack resistance. (D) The compound having a photopolymerizable double bond is a polymerizable monomer containing at least one photopolymerizable double bond group in one molecule.

Examples of the compound (D) having a photopolymerizable double bond include polyethylene glycol di (meth) acrylate [number of ethylene glycol units 2 to 20], poly (1,2-propylene glycol) di (meth) , The number of 2-propylene glycol units 2 to 20], polytetramethylene glycol di (meth) acrylate [number of tetramethylene glycol units 2 to 10], tri-2-hydroxyethylisocyanurate tri (meth) (Meth) acrylic acid adduct, methylene bisacrylamide, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, bisphenol A diglycidyl ether- (Meth) acrylate modified with isophthalic acid, pentaerythritol tri (meth) acrylate modified with N, N'-bis (2-methacryloyloxyethyl) , Terephthalic Acid-modified pentaerythritol tri (meth) acrylate, dimethacrylate of polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A, and bisphenol A, (Meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (Meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, 1,4-cyclohexanediol di Acrylate, glycerol tri (meth) acrylate, trimethylol propyl Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylol propane tri (meth) acrylate, trioctyl trimethylol propane triacrylate, pentaerythritol tetra (Meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate and? -Hydroxypropyl-? '- (acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxybutyl Benzene, add 2-hydroxy-3-phenoxypropyl caproic lactone acrylate or these monomers may be mentioned water or the like.

The compound (D) having a photopolymerizable double bond may further contain a carboxyl group. Examples of the compound having a photopolymerizable double bond (D) further containing a carboxylic acid include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- Succinic acid, 2- (meth) acryloxyethylhexahydrophthalic acid, 2- (meth) acryloxyethylphthalic acid, 2,2,2-triacryloyloxymethylethyl succinic acid and the like. These may be used alone or in combination of two or more.

The content of the compound having a photopolymerizable double bond (D) is preferably 5 parts by mass or more, more preferably 5 parts by mass or more, from the viewpoint that each component sufficiently crosslinks to exhibit adhesion to the substrate, relative to 100 parts by mass of the total solid content in the polysiloxane composition. Preferably not less than 10 parts by mass, and not more than 45 parts by mass, more preferably not more than 40 parts by mass, from the viewpoint of reduction of residues after development.

<(E) Ultraviolet absorber>

In the present embodiment, it is preferable to add the ultraviolet absorber (E) to the polysiloxane composition in order to improve the light resistance of the polysiloxane composition and reduce the residue upon development. It is also preferable to use (E) ultraviolet absorber in combination with (C) a nitroxy compound because the resolution of the polysiloxane composition can be greatly improved. Examples of the ultraviolet absorber (E) include benzotriazole-based compounds and benzophenone-based compounds. Specific examples of the ultraviolet absorber (E) include 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) (2H-benzotriazol-2-yl) -4,6-dihydroxybenzoic acid ester (TINUVIN405 manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- Dodecyl-4-methylphenol, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole and 2-hydroxy-4-methoxybenzophenone.

The content of the ultraviolet absorber (E) in the case of adding the ultraviolet absorber (E) to the polysiloxane composition is preferably 0.01 part by mass or more from the viewpoint of preventing curing of the unexposed portion, relative to 100 parts by mass of the total solid content in the polysiloxane composition , More preferably not less than 0.1 part by mass, and is preferably not more than 10 parts by mass, more preferably not more than 5 parts by mass from the viewpoint of pattern formation due to radical generation during exposure.

<(F) Alkali-soluble resin>

In the present embodiment, the polysiloxane composition preferably further comprises (F) an alkali-soluble resin. When the polysiloxane having a radical crosslinkable group has an alkali-soluble group and alkali development of the polysiloxane composition is possible, (F) an alkali-soluble resin is preferably added to the polysiloxane composition.

The (F) alkali-soluble resin refers to an alkali-soluble resin having an alkali-soluble group and having an acid value of 10 to 200 mgKOH / g.

From the viewpoint of compatibility, the acid value of the alkali-soluble resin (F) is preferably close to that of the polysiloxane (A) having a radical crosslinkable group, and is preferably 10 mgKOH / g or more, more preferably 10 mgKOH / g or more Is preferably not less than 20 mgKOH / g, and more preferably not more than 200 mgKOH / g, more preferably not more than 190 mgKOH / g, from the viewpoint of pattern adhesion.

(F) The alkali-soluble resin is not particularly limited as long as it has an alkali-soluble group and an acid value of 10 to 200 mgKOH / g, but it is also possible to use a resin having a carboxyl group, a dicarboxylic acid anhydride group or a dicarboxylic acid anhydride group- . Since the polysiloxane composition (F) contains a carboxyl group in the alkali-soluble resin, it exhibits alkali solubility while maintaining heat-resistant transparency, and good film properties can be obtained.

The content of the alkali-soluble resin (F) is not particularly limited and may be arbitrarily selected depending on the desired film thickness or application. From the viewpoint of heat crack resistance, it is preferably 1 part by mass or more based on 100 parts by mass of the total solid content in the polysiloxane composition More preferably not less than 5 parts by mass, still more preferably not less than 10 parts by mass, and on the other hand, from the viewpoint of heat resistance and transparency, it is preferably not more than 50 parts by mass, more preferably not more than 45 parts by mass, Is not more than 40 parts by mass.

(F) The alkali-soluble resin has an alkali-soluble group, and the following (1) to (5):

(1) a vinyl polymer mainly composed of a polymerizable double bond reactant,

(2) an epoxy polymer composed mainly of an addition reaction product of an epoxy group and a hydroxyl group,

(3) an aromatic methylene polymer mainly composed of a reaction product of phenol and formaldehyde,

(4) a urethane polymer composed mainly of a reaction product of a dialcohol and a diisocyanate, and

(5) an ester polymer composed mainly of a reaction product of a dicarboxylic acid and a diepoxide

And at least one kind of polymer selected from the group consisting of On the other hand, in the polymers (1) to (5), the term "main component" means a component containing 70 mol% or more of the component in the molecule.

Among the above polymers (1) to (5), particularly (1) and (3) will be described in detail below.

(1) a vinyl polymer mainly composed of a polymerizable double bond reactant

For example, a carboxyl group-containing vinyl polymer represented by the following chemical formula (4) or chemical formula (6) may be mentioned.

Wherein Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms and Re is a group represented by the following formula (5):

(Wherein Rb represents a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms or a monovalent organic group having a photopolymerizable double bond group, and Rc is a group represented by the following formula (3):

(Wherein R < a > is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms) or hydrogen, and Rf is A straight chain, branched chain or cyclic monovalent organic group having 1 to 20 carbon atoms, Rh is independently a methyl group or hydrogen, m is an integer selected from 1 to 500, and n is selected from 10 to 1,000 Is an integer.]

(Wherein Rb represents a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms or a monovalent organic group having a photopolymerizable double bond group and Rc is a group represented by the formula (5) Rf is a divalent organic group which may have a straight chain, branched chain or cyclic divalent organic group having 0 to 20 carbon atoms or may have a photopolymerizable double bond, Rf is a divalent organic group having 1 to 20 carbon atoms, R is a methyl group or a hydrogen, m is an integer selected from 1 to 500, and n is an integer selected from 10 to 1,000, wherein R is a linear, branched or cyclic monovalent organic group of 1 to 20 carbon atoms,

Examples of the method for obtaining a carboxyl group-containing vinyl polymer include the following three methods:

(meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide and hydrogen on the nitrogen thereof, (Meth) acrylonitrile and (meth) acrylic acid glycidyl is subjected to vinyl copolymerization in the presence of a catalyst, wherein the compound (b) is copolymerized with at least one compound selected from the group consisting of styrene and styrene derivatives.

(ii) at least one compound (c) selected from a compound having a carboxyl group of a vinyl polymer and an epoxy group and a (meth) acrylic group in a molecule after the compound (a) and the compound (b) A method of adding reaction.

(iii) vinyl polymerizing the compound (b) and the compound (c), then subjecting the compound (a) to an addition reaction with an epoxy group of the vinyl polymer, and adding a dicarboxylic acid anhydride Lt; / RTI >

(Meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acrylate and the like can be given as examples of the compound (Meth) acryloxyethylhexahydrophthalic acid, 2- (meth) acryloxyethylphthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and maleic acid half-ester. These may be used alone or in combination of two or more.

Examples of the compound (b) used for preparing the carboxyl group-containing vinyl polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, propyleneglycol mono (meth) acrylate, (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylamide, N-methylol acrylamide, N-butoxymethylacrylamide, styrene,? -Methylstyrene, p-methylstyrene, ) Acrylate, Acrylate, 4-methoxybenzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate, (meth) acrylonitrile, glycidyl 3- (meth) acryloylpropyltrimethoxysilane, 3- (meth) acryloxymethyloxetane, hexafluoropropyl (meth) acrylate, 3- Methacryloylpropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The compound (c) used for preparing the carboxyl group-containing vinyl polymer is not particularly limited as long as it is a half-ester of an epoxy (meth) acrylate obtained by reacting an epoxy resin having two epoxy groups with (meth) acrylic acid by a usual method Do not. Examples of the compound (c) include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, vinylcyclohexene monoxide , Half-esters of (meth) acrylic acid, bisphenol-A type epoxy resins, bisphenol-F (meth) acrylate, Bisphenol-S type epoxy resins, epoxy compounds of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and the like, (Meth) acrylic acid, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) , Epoxy compounds of 1,3,3,3-hexafluoropropane, and the like. A half-ester of a (meth) acrylic acid and an alicyclic diglycidyl ether compound such as a cyclohexanedimethanol diglycidyl ether compound and a half-ester of (meth) acrylic acid, a 1,6-hexanediol di Aliphatic diglycidyl ether compounds such as glycidyl ether, 1,4-butanediol diglycidyl ether and diethylene glycol diglycidyl ether, and half-esters of (meth) acrylic acid. These may be used alone or in combination of two or more.

Examples of the compound (d) used for preparing the carboxyl group-containing vinyl polymer include succinic anhydride, cyclohexanedicarboxylic acid anhydride, 4-methyl-cyclohexanedicarboxylic acid anhydride, 5-methylcyclohexanedicarboxylate (3-tert-butylcycloheptanedicarboxylic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, 3- (Trimethoxysilylpropyl) succinic anhydride, and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

The vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a conventional method, and known methods such as solution polymerization, suspension polymerization and emulsion polymerization can be used, but solution polymerization is preferable because of easy handling. As the polymerization initiator that can be used at this time, it is preferable that the 10-hour half-life temperature is within the range of 60 占 폚 to 120 占 폚. Examples of such a polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutylnitrile Azo compounds such as 2,2'-azobis (2-methylpropionate), 2,2'-azobis (N-cyanohexyl- 2-propenyl) -2-methylpropionamide), and the like, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t- T-butylperoxy benzoate, t-butyl peroxyacetate, t-butyl peroxy-m-tolyl benzoate, t-butyl Peroxybenzoates and the like, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymonocarbonates such as peroxy isopropyl monocarbonate and t-butyl peroxy-2-ethylhexyl monocarbonate, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Diacyl peroxides such as diacyl peroxide, diacyl peroxide, and p-chlorobenzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and t-butyl cumyl peroxide; and the like. These may be used alone or in combination of two or more.

The addition reaction of a carboxyl group with a compound having an epoxy group and a (meth) acrylic group in the preparation of a carboxyl group-containing vinyl polymer is preferably carried out in a solvent using a polymerization inhibitor and a catalyst, and the reaction temperature is preferably 50 ° C Deg.] C to 120 [deg.] C.

Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Acetic acid esters; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated naphtha and solvent naphtha. These may be used alone or in combination of two or more.

Examples of the reaction catalyst for the above reaction in the preparation of the carboxyl group-containing vinyl polymer include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, and 2-ethyl-4-methylimidazole Phosphorus compounds such as imidazole compounds and triphenylphosphine, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octenoic acid. These may be used alone or in combination of two or more.

Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine and the like. These may be used alone or in combination of two or more.

In addition, a dicarboxylic acid anhydride may be partially added to the hydroxyl group of the reaction product, and the reaction temperature is preferably 50 to 120 ° C.

(3) an aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde

Examples of the polymer (3) include novolak type phenol polymers represented by the following formula (9).

(Wherein Rb represents a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms or a monovalent organic group having a photopolymerizable double bond group and Rc represents a group represented by the above formula (5) or Hydrogen, Rj is a methyl group, a hydroxyl group or hydrogen, and Rk is a group represented by the formula (5) or the following formula (8):

M is an integer selected from 0 to 100, and n is an integer selected from 4 to 1,000.

The novolac phenolic polymer used in the present embodiment is obtained by reacting epihalohydrin with a condensation reaction product of phenol and formaldehyde. The (meth) acrylate compound having a carboxyl group or a hydroxyl group may be additionally reacted with the epoxy group of the reactant, and the hydroxyl group of the reactant may be reacted with the dicarboxylic acid anhydride.

Examples of the phenol used for preparing the novolak-type phenolic polymer include phenol, cresol, xylenol, trimethylphenol and the like. These may be used alone or in combination of two or more.

Examples of the epihalohydrin used in the novolak-type phenolic polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.

Examples of the compound having a carboxyl group and a (meth) acrylate group in a molecule used for preparing the novolac phenolic polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, Acrylate, 2- (meth) acryloxyethyl succinate, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and maleic acid half- And the like. These may be used alone or in combination of two or more.

Examples of the hydroxyl group and (meth) acrylate compound used in the preparation of the novolac phenolic polymer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylate, glycerol mono (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy- Di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, and caprolactone adducts of these monomers.

Examples of the (meth) acrylate-modified epoxy (meth) acrylate compound having an epoxy group modified include phenyldiglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether and resorcinol diglycidyl ether Bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) (Meth) acrylate, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, and hydrogenated bisphenol type epoxy resin such as epoxy compound of 3,3-hexafluoropropane, Epoxy (meth) acrylates of hydrogenated bisphenol type epoxy compounds such as epoxy compounds of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, Methanol diglycidyl ether compound (Meth) acrylate, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether of an alicyclic diglycidyl ether compound And epoxy (meth) acrylates of aliphatic diglycidyl ether compounds.

Examples of the dicarboxylic acid anhydrides used for preparing the novolak-type phenolic polymer include succinic anhydride, cyclohexanedicarboxylic acid anhydride, 4-methyl-cyclohexanedicarboxylic acid anhydride, 5-methyl-cyclohexanedicarboxylic acid Anhydrides, anhydrides, phthalic anhydrides, phthalic anhydrides, (3-tri (tetrabutylphthalic anhydride), triphenylphthalic anhydride, trimellitic anhydride, pyromellitic anhydride, (Methoxysilylpropyl) succinic anhydride, and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

When condensation reaction of phenol and formaldehyde is carried out in the preparation of the novolac phenolic polymer, it is preferable to use an acid catalyst. Various acid catalysts can be used, and examples thereof include hydrochloric acid, sulfuric acid, p- toluenesulfonic acid, oxalic acid, boron trifluoride , Anhydrous aluminum chloride, zinc chloride and the like are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable.

The condensation reaction of phenol and formaldehyde can be carried out under a solventless condition or in the presence of an organic solvent. Specific examples of the organic solvent include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, and the like. The amount of the organic solvent to be used is usually 50% by mass to 300% by mass, preferably 100% by mass to 250% by mass, based on the total mass of the input raw materials. The reaction temperature is usually 40 ° C to 180 ° C, and the reaction time is usually 1 hour to 10 hours. These solvents may be used alone, or two or more solvents may be used in combination.

After completion of the reaction, the water washing treatment is carried out until the pH value of the water washing liquid of the reaction mixture becomes 3-7, preferably 5-7. In the case of washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogenphosphate, further diethylenetriamine, triethylenetetramine, aniline, phenyl And various basic substances such as organic amines such as lanediamine may be used as a neutralizing agent. In the case of the water washing treatment, it may be carried out according to a usual method. For example, water obtained by dissolving the neutralizing agent is added to the reaction mixture, and the liquid extraction operation is repeated, and the solvent is distilled off under reduced pressure heating to obtain the product.

An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a molten mixture of a condensate of phenol and formaldehyde obtained by the above reaction and an epihalohydrin such as epichlorohydrin or epibromohydrin, At 120 DEG C for 1 hour to 10 hours to obtain an epoxy resin. Epihalohydrin or other addition solvent or the like is removed from the reaction product of the epoxidation reaction at 110 ° C to 250 ° C and a pressure of 10 mmHg or less, without rinsing or without rinsing under heating and decompression. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is further added, , It is possible to make the closing ring reliable. The reaction temperature is usually 50 ° C to 120 ° C, and the reaction time is usually 0.5 hours to 2 hours.

After the completion of the reaction, the resulting salt is removed by filtration, washing with water, and the solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.

The addition reaction of the epoxy group in the preparation of the novolak-type phenolic polymer with a carboxyl group or a compound having a hydroxyl group and a (meth) acrylic group is preferably carried out in a solvent using a polymerization inhibitor and a catalyst, Is preferably performed at 50 ° C to 120 ° C.

In the preparation of the novolak-type phenolic polymer, the reaction solvent, the reaction catalyst and the polymerization inhibitor may be the reaction solvent, the reaction catalyst and the polymerization inhibitor described in the preparation of the vinyl polymer mainly composed of the reactant of the above polymerizable unsaturated double bond, Reaction catalyst and polymerization inhibitor may be used.

In addition, a dicarboxylic acid anhydride may be partially added to the hydroxyl group of the reaction product, and the reaction temperature is preferably 50 ° C to 120 ° C.

From the viewpoint of the heat resistance of a reactant mainly composed of a polymer, the alkali-soluble resin is preferably a copolymer of a vinyl polymer mainly composed of a reaction product of a polymerizable unsaturated double bond, an epoxy polymer composed mainly of an addition reaction product of an epoxy group and a hydroxyl group, Is an at least one kind of polymer selected from the group consisting of an aromatic methylene polymer composed mainly of a reaction product of a reaction product of a dicarboxylic acid and a diepoxide and an ester polymer composed mainly of a reaction product of a dicarboxylic acid and a diepoxide.

The ratio of the acid value (A) / acid value (F) of the acid value (A) (mgKOH / g) of the polysiloxane having a radical crosslinkable group to the acid value (F) (mgKOH / g) of the alkali- Is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more, from the viewpoint of compatibility with the polarity of the polysiloxane having a crosslinkable group and the alkali-soluble resin (F) It is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less.

<(G) Silane coupling agent>

A silane coupling agent may be added to the polysiloxane composition in order to improve the adhesion between the cured film and the substrate after exposure and development of the polysiloxane composition. Examples of the silane coupling agent include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- Styryltrimethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane, p- (2-propenylphenyl) triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) tri (methoxycyclohexyl) trimethoxysilane, 3- Epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- 2- (Ami Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, , N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, hydrochloride of N- (vinylbenzyl) Mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- 3-mercaptopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, De, and 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-ethoxy-silyl propyl succinic anhydride in the tree.

When the silane coupling agent is added to the polysiloxane composition, the content of the silane coupling agent is preferably at least 0.1 part by mass, more preferably at least 0.1 part by mass, from the viewpoint of developing the adhesiveness to the substrate with respect to 100 parts by mass of the total solid content in the polysiloxane composition Is preferably not less than 0.5 part by mass, and is preferably not more than 20 parts by mass, more preferably not more than 15 parts by mass, from the viewpoint of curing reactivity of the polysiloxane composition.

&Lt; (I) Solvent >

In the present embodiment, it is preferable to add a solvent to the polysiloxane composition and adjust its viscosity from the viewpoint of adjusting the coating film thickness. Suitable solvents include the following solvents (1) to (6):

(1) aliphatic alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, -Hexanol, isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, Nonyl alcohol, 3,5,5-trimethylhexanol, 1-decanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-heptecanol, 1-dodecanol, isododecyl alcohol, Alcohol, propargyl alcohol, hexynol

(2) aromatic alcohols such as benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) Diethanol, 1-phenylethanol, 2-phenyl-3-methoxyphenyl) methanol, (4-methoxyphenyl) methanol, Propanol, p-tolyl alcohol, 2- (4-hydroxy-3-methoxyphenyl) ethan-1-ol, 2- (3,4-dimethoxyphenyl) ethan- Propan-2-ol, cinnamyl alcohol, 3- (4-hydroxy-3-methoxyphenyl) 1-ol, diphenylmethanol, trityl alcohol, 1,2-diphenylethane-1,2-diol, 1,1,2,2- -Tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3-dimethanol, benzene-

(3) Alicyclic alcohols: Cyclohexanol, methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydro-2-furan methanol

(4) Glycols or derivatives thereof: ethylene glycol, ethylene glycol monoalkyl (1 to 8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (1 to 6) ethers, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, Propylene glycol monophenyl ether, dipropylene glycol monoalkyl ether (having 1 to 3 carbon atoms), ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, Propylene glycol monoacrylate, propylene glycol monoacetate

(5) Ketone compounds: acetone, methyl ethyl ketone, 3-butyne-2-one, methyl n-propyl ketone, methyl isopropyl ketone, Butyl ketone, methyl isobutyl ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl- 2-octanone, 3-octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutyl ketone, trimethylnonanone, 2,4- 5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone, isophorone

(6) Others: N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylsulfoxide, Lactone,? -Acetyl-? -Butyrolactone, tetramethyl urea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone

These may be used alone or in combination of two or more. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable from the viewpoint of evaporating the solvent by heating the coating film .

These solvents can be appropriately added to the polysiloxane composition depending on the coating film thickness and viscosity, and it is preferable to use them in a range of 50 to 1,000 parts by mass with respect to 100 parts by mass of the solid components in the polysiloxane composition.

In the present embodiment, a surfactant may be contained in the polysiloxane composition in order to ensure the application suitability of the polysiloxane composition and the film smoothness after drying. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like Polyoxyethylene alkylaryl ethers such as polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylphenyl ethers such as polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylphenyl ethers such as polyoxyethylene alkylphenyl ethers, Fluorine surfactants such as CF430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surfron S-382, SC-101, 102, 103, 104 and 105 (manufactured by Asahi Glass), DBE-712, DBE821 (Trade name, manufactured by Cytec), and the like.

The content of these surfactants is preferably not less than 0.01 part by mass, more preferably not less than 0.1 part by mass, from the viewpoint of application suitability and residue reduction, relative to 100 parts by mass of the total solid content in the polysiloxane composition, It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less from the viewpoint of adhesion.

In order to improve the thermal stability and the storage stability of the polysiloxane composition, a polymerization inhibitor (for example, a radical polymerization inhibitor) may be contained in the polysiloxane composition. Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine disuccinic acid, 1,2- Glycol ether diaminic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-ditert-butyl) phenylmethane and the like.

The content of the polymerization inhibitor in the case of adding the polymerization inhibitor to the polysiloxane composition is preferably 0.001 part by mass or more from the viewpoint of exhibiting the polymerization inhibiting effect of the photopolymerizable double bond relative to 100 parts by mass of the total solid content in the polysiloxane composition More preferably 0.01 part by mass or more, and is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, from the viewpoint of pattern formation due to radical generation during exposure.

&Lt; (H) Antioxidant >

In this embodiment, an antioxidant may be added to the polysiloxane composition to improve the thermal stability of the polysiloxane composition in the presence of oxygen. Examples of such an antioxidant include hindered phenol-based, phosphorus-based, lactone-based, vitamin E-based, and sulfur-based ones.

Specific examples of the antioxidant include, but are not limited to, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245, (IRGANOX259, manufactured by BASF), 2,4-bis- (n-octylthio) -2,3,5,6-tetramethyluronium hexafluorophosphate (IRGANOX565, manufactured by BASF), pentaerythritol tetrakis [3- (3,5-dihydroxy-3,5-di- Di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1010 manufactured by BASF), 2,2-thio-diethylenebis [3- (3,5- (IRGANOX1035 manufactured by BASF Corporation), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (3,5-di-t-butyl-4-hydroxy-hydrosinnamide) (IRGANOX1098, manufactured by BASF), 3,5-di-t-butyl-4-hydroxybenzylphosphonate - diethyl ester (B (3,5-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX1330 manufactured by BASF), tris- (3,3- (IRGANOX3114, manufactured by BASF), octyldiphenylamine (IRGANOX5057, manufactured by BASF), 2,4-bis [(octylthio) methyl) (IRGANOX 1520L manufactured by BASF Corporation), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1135 manufactured by BASF), 2,4- Methylphenol (IRGANOX1726, manufactured by BASF), 2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) chroman-6-ol IRGANOX E201), 5,7-di-t-butyl-3- (3,4-dimethylphenyl) benzofuran-2 (3H) Butylphenyl) phosphite (IRGAFOS168 manufactured by BASF), tris [2- [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, 6-yl] oxy] ethyl] amine (IRGAFOS12 manufactured by BASF), bis (2,4-di-t-butyl- (IRGANOX PS80 manufactured by BASF), 3,3-thiobisopropionic acid dioctadecyl ester (IRGANOX PS802 manufactured by BASF), and the like .

Specific examples of the antioxidant include, but are not limited to, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (SUMILIZER GA-80 manufactured by Sumitomo Chemical Co., Ltd.), 2,2'-methylenebis (6-t- (SUMILIZER MDP-S manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-butylidenebis (6-t-butyl-3-methylphenol) (SUMILIZER WX-R, manufactured by Sumitomo Chemical Co., Ltd.), pentaerythritol-tetrakis (3-laurylthiopropionate) (Sumitomo Chemical Co., (SUMILIZER TP-D manufactured by Kusa Co.), 2-mercaptobenzimidazole (SUMILIZER MB manufactured by Sumitomo Chemical Co., Ltd.), biphenyl-4,4'-diyl-bis [bis (2,4- -Methylphenoxy) phosphine (GSY-P101 manufactured by Osaka Kyoeisha), cyclohexane and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6 -T Chloro-1,3,5-triazine and the reaction product is the reaction product of 2-aminoethanol and the and the like (BASF Corp. TINUVIN152).

These antioxidants may be used alone or as a mixture of two or more thereof. When the antioxidant is added to the polysiloxane composition, the content of the antioxidant is preferably 0.001 part by mass or more, more preferably 0.001 part by mass or more from the viewpoint of exhibiting the thermal stability effect in the presence of oxygen with respect to 100 parts by mass of the total solid content in the polysiloxane composition Is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of pattern formation property due to radical generation during exposure Is not more than 5 parts by mass.

The polysiloxane composition may contain an additive such as a plasticizer if necessary. Examples of such additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri- n-butyl, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. The content of the plasticizer when the plasticizer is added to the polysiloxane composition is preferably not less than 0.1 part by mass, more preferably not less than 0.5 part by mass, from the viewpoint of increasing the flexibility of the film, relative to 100 parts by mass of the total solid content in the polysiloxane composition More preferably 0.7 part by mass or more, and in view of the glass transition temperature, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, furthermore preferably 5 parts by mass or less.

The acid value of the polysiloxane composition used in this embodiment is preferably 0.1 mgKOH / g or more, more preferably 1 mgKOH / g or more, still more preferably 5 mgKOH / g or more from the viewpoints of reduction of residue after development and crack resistance of the cured film. is preferably not less than 200 mgKOH / g, more preferably not more than 170 mgKOH / g, still more preferably not more than 150 mgKOH / g, from the viewpoint of pattern adhesion.

&Lt; Cured product of photosensitive resin composition >

In the cured product obtained by curing the polysiloxane composition used in the present embodiment, the cured product having a thickness of 10 탆 preferably has a light transmittance of 70% or more at a wavelength of 400 nm after being baked at 220 캜 for 3 hours under the atmosphere Do. It is also preferable to obtain a transparent insulating film by curing the polysiloxane composition used in the present invention.

The radical content in the cured product is preferably 0.1 × 10 ^-6 mol or more, more preferably 0.15 × 10 ^-6 mol or more, per 1 g of the cured product. On the other hand, from the viewpoint of pattern formation is 120 × 10 ^-6 mol or less is preferable, more preferably 60 × 10 ^-6 mol or less. The method of measuring the radical content in the cured product is the same as that described above for the polysiloxane composition.

A suitable example of a method of forming a cured relief pattern using the above polysiloxane composition will be described below.

A method for forming a cured relief pattern includes a first step of applying a polysiloxane composition on a substrate, a second step of irradiating an actinic ray, a third step of removing an uncured portion with a developing solution, and a fourth step of heating and curing .

First, the polysiloxane composition is applied onto various desired substrates such as a silicon wafer, a ceramic substrate, and an aluminum substrate. As a coating apparatus or a coating method, a spin coater, a die coater, a spray coater, an immersion, a printing, a blade coater, a roll coating, or the like can be used. The applied substrate is soft baked at 80 to 200 DEG C for 1 to 15 minutes and then irradiated with an actinic ray through a desired photomask using an exposure projection apparatus such as a contact aligner, a mirror projection, and a stepper.

As the active ray, X rays, electron rays, ultraviolet rays, visible rays, or the like can be used. In the present invention, those having a wavelength of 200 nm to 500 nm are preferably used. In view of resolution and handling of the pattern, the light source wavelength is preferably the UV-i line (365 nm), and a stepper is particularly preferable as the exposure projection apparatus.

Thereafter, for the purpose of improving the photosensitivity and the like, a post-exposure baking (PEB) process with arbitrary temperature and time combination (preferably, a temperature of 40 ° C to 200 ° C and a time of 10 seconds to 360 seconds) ), Or pre-development baking may be performed.

Subsequently, development can be performed by a method such as a dipping method, a puddle method, a shower method, and a rotary spray method. As the developer, an organic solvent or an alkaline developer is preferable. The positive solvent of the composition of the present invention may be used alone or in a mixture of a good solvent and a poor solvent.

Suitable examples of the alkali developing solution include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, ammonium hydroxides such as tetraethylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution, diethylamine, triethylamine, Amines such as diethanolamine, triethanolamine and the like. Particularly preferred are ammonium hydroxide such as sodium carbonate, potassium carbonate, lithium carbonate and the like, tetramethylammonium hydroxide and tetraethylammonium hydroxide, weakly alkaline compounds containing 0.05% by mass to 10% by mass of amines such as diethylamine and diethanolamine, It is preferable to use an aqueous solution for development at a temperature of 20 ° C to 35 ° C.

Examples of the developer for the organic solvent include ethylene glycol, propylene glycol and the like in the glycol, and examples of the monoalkyl ether of the glycol include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol monoethyl ether, and the like. Examples of the developer for the other organic solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N- Lactone,? -Acetyl-gamma butyrolactone, cyclopentanone, cyclohexanone, and the like.

After completion of the development, the resist film is rinsed with a rinsing liquid, and the developer is removed to obtain a coating film having a relief pattern. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, etc. may be used alone or in an appropriate mixture, or they may be used in combination in stages.

The relief pattern thus obtained is converted into a cured relief pattern at a curing temperature which is much lower than that of a conventional polyimide precursor composition of 150 ° C to 250 ° C. The heating and curing can be performed by using a hot plate, an inert oven, a heating oven capable of setting a temperature program, or the like. As the atmospheric gas at the time of heating and curing, air may be used, and if necessary, an inert gas such as nitrogen or argon may be used.

The above-described curing relief pattern can be used for the surface protective film of a semiconductor device formed on a substrate such as a silicon wafer, a glass, a film, a substrate sputtered with one or more kinds of metal, an interlayer insulating film, (Partition wall) between the structure and the package material, and the other process uses an optical element such as a touch panel or a CMOS image sensor by applying the well-known manufacturing method of the semiconductor device , Various display devices, and semiconductor devices can be manufactured. In addition, an electronic component or a semiconductor device having a coating film made of a resin obtained by curing the above polysiloxane composition can be obtained.

Example

Hereinafter, the method of the embodiment will be described concretely according to the examples, but the present invention is not limited by the following examples.

(ESR measurement method)

ESR was measured in a state where the sample was shielded from light with a wavelength of 400 nm or less under an atmospheric pressure, 24 ° C, and atmospheric pressure, using an ESR (model: JES-FE2XG) manufactured by Nihon Denshsai Co., As a standard sample marker, a manganese marker (Mn ²⁺ ) was used.

Measurement conditions of the apparatus are shown below.

Microwave power: 1 mW

Modulation field: 1 G

Response: 0.03 second

Amplitude: 200 or more

Magnetic field: 3380 G

Hatchability: ± 250 G

Hours: 4 minutes

After the ESR device was adjusted, only acetone was placed in the ESR sample tube (flat cell), and Amplitude was set to 1000, and it was confirmed that only 6 peaks of Mn ² ⁺ were visible as shown in FIG. 1 .

The third peak counted from the author section of Mn ² ⁺ side with the standard peak and, on the g3 = 2.034, is used when calculating the value g of the measurement sample. The fourth peak counted from the author's side is g4 = 1.981.

A 1 ppm acetone solution of 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared and measured by ESR , It was confirmed that a peak of 4-hydroxy-TEMPO was observed as shown in Fig.

As a standard peak, the peak of 6 of Mn ² ⁺ is used, and the third peak counted from the author side. Assuming that the absorption field of the standard peak is H _s , g _s is 2.034, and the absorption magnetic field of the measurement sample is H ₀ . The g value of the measurement sample was calculated by the following equation.

g = g _s + g _s (H _s -H ₀ ) / H _s

In a 20 mL sample tube, 1 g of polysiloxane and 9 g of acetone were weighed, dissolved and capped. Thereafter, the sample was allowed to stand for 24 hours in a state of shielding light having a wavelength of 400 nm or less under atmospheric pressure at 24 캜 under atmospheric pressure, and ESR was measured.

&Lt; Measurement of Resin Composition >

In a 20 mL sample tube, 0.3 g of the resin composition and 9.7 g of acetone were weighed and covered. Thereafter, the sample was allowed to stand for 24 hours in a state of shielding light having a wavelength of 400 nm or less under atmospheric pressure at 24 캜 under atmospheric pressure, and ESR was measured.

Hydroxy TEMPO was used as a sample having one mole of the radical per mole of the molecule to prepare a calibration curve and the concentration of radicals in the solution was analyzed. With respect to the polysiloxane composition and the photosensitive resin composition, the thermogravimetric loss in which 10 mg of the sample was held at 250 캜 for 30 minutes was measured using TGA, and the remaining solid content was analyzed for the solid content. The amount of radicals contained per g of the solid content was calculated from the radical concentration and the solid content content obtained by measurement of the resin composition.

(Assessment Methods)

1. Evaluation of resolution

The photosensitive resin composition was coated on a silicon substrate sputtered with aluminum so that the film thickness after baking became 15 占 퐉, and baked on a hot plate at 95 占 폚 for 4 minutes.

The substrate having the above-mentioned coating film was exposed using an i-line stepper (NSR2005 i8A manufactured by Nikon Corporation) through a reticle having a test pattern. The exposure was performed in the atmosphere, and the focus was set at -15, and irradiation was performed at a pitch of 30 mJ / cm < 2 > from 60 mJ / cm2 to 1110 mJ / cm2.

(With respect to Examples 1 to 14, Examples 16 to 27 and Comparative Examples 1 to 5)

Subsequently, the resist film was developed under the conditions of 23 ° C for 30 seconds × 2 times using an alkali developing solution (developer of AZ ELECTRONIC MATERIALS, 2.38% tetramethylammonium hydroxide aqueous solution) and rinsed with pure water to form an unexposed portion Removed. Subsequently, the substrate patterned above was baked at 220 캜 for 30 minutes in an oven substituted with nitrogen and cured.

(Regarding Example 15)

Following exposure, development was carried out using PGMEA (propylene glycol monomethyl ether acetate) at 23 캜 for 30 seconds × 2 times to remove unexposed portions of the coated film. Subsequently, the substrate patterned above was baked at 220 캜 for 30 minutes in an oven substituted with nitrogen and cured.

The portions shaded with a square of 25 m x 25 m in an exposure amount of 400 mJ / cm < 2 > of the patterns obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were observed with an optical microscope and evaluated according to the following criteria.

○: No residue and open, no floating or peeling observed in the pattern

?: Opened but with some residue, no floating or peeling observed in the pattern

X: Residual, not open, or floating or peeling of pattern

2. Evaluation of maritime scope

The pattern obtained above was observed with an optical microscope to determine the range of the exposure amount which was free from residue and opened and which did not cause floating or peeling in the pattern as a marginal area in the portion shaded with a square of 25 mu m x 25 mu m , And evaluated based on the following criteria.

◎: Wider than the range of 420 mJ / ㎠

○: Wider than marine range of 300 mJ / ㎠

?: Wider than the sea area of 120 mJ / cm 2

X: The marine area is 120 mJ / cm 2 or less

3. Evaluation of crack resistance

The polysiloxane composition was coated on a silicon substrate which had been aluminum sputtered to a thickness of 15 mu m after baking, and baked on a hot plate at 95 DEG C for 4 minutes.

The substrate having the above-mentioned coating film was subjected to 400 mJ / cm2 exposure using an i-line stepper through a reticle having a test pattern. The exposure was performed in the atmosphere, and the focus was set at -15.

(Regarding Example 15)

Subsequent to exposure, development was carried out using PGMEA under the conditions of 23 占 폚, 30 seconds 占 2 times to remove unexposed portions of the coating film. Subsequently, the substrate patterned above was baked at 220 캜 for 30 minutes in an oven substituted with nitrogen and cured.

The patterned substrates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were further baked at 300 占 폚 for 30 minutes in an oven replaced with nitrogen and then baked at -40 占 폚 for 15 minutes and at 120 占 폚 A cycle of one cycle of 15 minutes was repeated 100 times, and then it was visually confirmed and observed with an optical microscope, and evaluated by the following criteria.

◎: Cracks in 5 substrates were not confirmed

○: 1 to 5 cracks occurred in 5 substrates

?: 6 to 15 cracks were generated in the five substrates

X: 16 cracks were generated in five substrates

4. Evaluation of transmittance

The polysiloxane composition was applied on a glass substrate so that the film thickness after development was 10 占 퐉. Then, an i-line stepper was used to expose the entire surface to 400 mJ / cm 2 in the air.

Subsequently, development was carried out using an alkali developing solution (developer of AZ ELECTRONIC MATERIALS CO., LTD., 2.38% tetramethylammonium hydroxide aqueous solution) at 23 캜 for 30 seconds × 2 times and rinsed with pure water to remove the coating film surface did.

(Regarding Example 15)

Subsequent to exposure, development was carried out using PGMEA under the conditions of 23 占 폚, 30 seconds 占 2 times to remove the coating film surface.

The developed substrate was baked at 220 占 폚 for 6 hours in an oven using an oven. Using a spectrophotometer UV-1600 PC (manufactured by Shimadzu Corporation), a glass substrate without a coating film was placed on a reference portion, and a light transmittance of 800 nm to 300 nm was measured to confirm a light transmittance of 400 nm.

[Synthesis Example 1]

(Synthesis of polysiloxane a-1)

A 1 L eggplant-shaped flask was charged with a stirrer, 0.60 mole (173.14 g) of (3-trimethoxypropyl) succinic anhydride, Ba (OH) ₂ .H ₂ O (trade name: X-12-967C Shin- , 4.00 mmol (0.83 g) of powder (manufactured by SIGMA-ALDRICH) and 0.58 mol (20.30 g) of methanol were charged and stirred using a magnetic stirrer. Dimros was attached and the temperature was raised from room temperature to 75 캜 by using an oil bath and refluxed for 2.5 hours to open anhydrous succinic acid.

2.40 mol (432.52 g) of DPD (diphenylsilanediol) (Shin-Etsu Chemical Co., Ltd.), 1.40 mol (347.69 g) of MEMO (3-methacryloxypropyltrimethoxysilane) 0.61 mmol (0.10 g) of hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) (manufactured by Tokyo Chemical Industry Co., Ltd.) Methoxypropyl) succinic anhydride, and the mixture was stirred using a stirring blade and a three-one motor. And the temperature was raised from room temperature to 95 캜 using an oil bath. After 1 hour, the heating was continued, and the dim rods were removed and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. Heating was continued for 10 hours while maintaining the vacuum state, then returned to normal pressure and cooled to room temperature to obtain transparent polysiloxane (a-1, viscosity at 40 ° C is 83 Poise). When the ESR of the polysiloxane (a-1) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.56 x 10 < ^-6 > mol / g.

[Synthesis Example 2]

(Synthesis of polysiloxane a-2)

Polysiloxane (a-2, viscosity at 40 캜 was 25 Poise) was obtained in the same manner as in Synthesis Example 1 except that DPD in Synthesis Example 1 was changed to DCPD (dicyclopentylsilane diol). When the ESR of the polysiloxane (a-2) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.54 x 10 < ^-6 > mol / g.

[Synthesis Example 3]

(Synthesis of polysiloxane a-3)

(A-3, 40) was obtained in the same manner as in Synthesis Example 1, except that MEMO in Synthesis Example 1 was changed to 1.00 moles of MEMO (3-methacryloxypropyltrimethoxysilane) and 0.40 moles of phenyltrimethoxysilane. And a viscosity at 100 [deg.] C was 100 Poise). When the ESR of the polysiloxane (a-3) was measured, a peak having a g value of 2.007 was observed. The radical concentration in the solid content was calculated to be 0.56 x 10 < ^-6 > mol / g.

[Synthesis Example 4]

(Synthesis of polysiloxane a-4)

The procedure of Synthesis Example 1 was repeated except that the MEMO in Synthesis Example 1 was changed to 1.40 moles of MEMO (3-methacryloxypropyltrimethoxysilane) and 0.40 moles of styryltrimethoxysilane (KBM1403, manufactured by Shin-Etsu Chemical Co., Ltd.) The polysiloxane (a-4, viscosity at 40 캜 was 90 Poise) was obtained in the same manner. When the ESR of the polysiloxane (a-4) was measured, a peak having a value of g = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.53 x 10 < ^-6 > mol / g.

[Synthesis Example 5]

(Synthesis of polysiloxane a-5)

2.00 mol (432.52 g) of DPD (diphenylsilanediol) (Shin-Etsu Chemical Co., Ltd.), 2.00 mol (496.70 g) of MEMO (3-methacryloxypropyltrimethoxysilane) 0.63 g (0.10 g) of hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.00 mmol (0.83 g) of Ba (OH) ₂ .H ₂ O powder (manufactured by SIGMA-ALDRICH) And the mixture was stirred using a motor. And the temperature was raised from room temperature to 95 캜 using an oil bath. After 1 hour, the heating was continued, and the dim rods were removed and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. Heating was continued for 10 hours while maintaining the vacuum state, and then the pressure was returned to the atmospheric pressure, and the solution was cooled to room temperature to obtain a transparent polysiloxane (a-5, viscosity at 40 캜 is 75 Poise). When the ESR of the polysiloxane (a-5) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.51 x 10 < ^-6 > mol / g.

[Synthesis Example 6]

(Synthesis of polysiloxane a-6)

Polysiloxane (a-6, viscosity at 40 캜 was 83 Poise) was obtained in the same manner as in Synthesis Example 1 except that 4-hydroxy-TEMPO in Synthesis Example 1 was not added. When the ESR of the polysiloxane (a-6) was measured, no peak was observed in the range of g value 2.034 to 1.984.

[Synthesis Example 7]

(Synthesis of polysiloxane a-7)

0.30 mol (86.57 g) of (3-trimethoxypropyl) succinic anhydride was added to a 1 L eggplant-shaped flask, and a solution of Ba (OH) ₂ .H ₂ O (trade name: X-12-967C Shin- 2.00 mmol (0.41 g) of powder (manufactured by SIGMA-ALDRICH) and 0.29 mol (10.15 g) of methanol were put in the flask and stirred using a magnetic stirrer. Dimros was attached and the temperature was raised from room temperature to 75 캜 by using an oil bath and refluxed for 2.5 hours to open anhydrous succinic acid.

1.00 mole (198.29 g) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.70 mole (173.84 g) of MEMO (3-methacryloxypropyltrimethoxysilane), 4-hydroxy- 0.30 mmol (0.05 g) of TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylpiperidyl) (manufactured by Tokyo Chemical Industry Co., Ltd.), 3-trimethoxypropyl ) The total amount of succinic anhydride conversion product and 400 g of PGMEA (propylene glycol monomethyl ether acetate) were added and stirred using a stirring blade and a three-one motor.

Subsequently, a mixture of 36.00 g of distilled water and 4.67 g of 5 mol / L hydrochloric acid was added dropwise and stirred for 30 minutes.

And the temperature was raised from room temperature to 95 캜 using an oil bath. After 2 hours, the heating was continued, and the dim rods were removed and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol, water, and PGMEA. Heating was continued for 4 hours while maintaining the vacuum state, and then the pressure was returned to the atmospheric pressure, and the solution was cooled to room temperature to obtain a transparent polysiloxane (a-7, viscosity at 40 캜 is 50 Poise). When the ESR of the polysiloxane (a-7) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.60 x 10 < ^-6 > mol / g.

[Synthesis Example 8]

(Synthesis of polysiloxane a-8)

(0) -1,3-divinyl (1) was added to a 1 L flask in a dropping funnel, followed by addition of a stirrer, anhydrous anhyamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), trimethoxysilane -1,1,3,3-tetramethyldisiloxane complex solution (Sigma Aldrich) was added dropwise with stirring. And heated at 80 DEG C for 4 hours, followed by heating at 100 DEG C for 4 hours. After cooling, the mixture was purified by distillation to obtain a hydrosilylated compound A in anhydrous anhydrous acid.

0.60 mol (171.81 g) of Compound A, 4.00 mmol (0.83 g) of Ba (OH) ₂ H ₂ O powder (manufactured by SIGMA-ALDRICH) and 0.58 mol (20.30 g) of methanol were added to a 1 L egg- And the mixture was stirred using a magnetic stirrer. Dimros was attached and the temperature was raised from room temperature to 75 캜 by using an oil bath and refluxed for 2.5 hours to open anhydrous succinic acid.

2.40 mol (432.52 g) of DPD (diphenylsilanediol) (Shin-Etsu Chemical Co., Ltd.), 1.40 mol (347.69 g) of MEMO (3-methacryloxypropyltrimethoxysilane) 0.61 mmol (0.10 g) of hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) (manufactured by Tokyo Chemical Industry Co., Ltd.) Methoxypropyl) succinic anhydride conversion product was added thereto, and the mixture was stirred using a stirring blade and a three-one motor. And the temperature was raised from room temperature to 95 캜 using an oil bath. After 1 hour, the heating was continued, and the dim rods were removed and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. Heating was continued for 10 hours while maintaining the vacuum state, and then the pressure was returned to the atmospheric pressure, and the solution was cooled to room temperature to obtain a transparent polysiloxane (a-8, viscosity at 40 DEG C of 75 Poise). When the ESR of the polysiloxane (a-8) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.58 x 10 < ^-6 > mol / g.

[Synthesis Example 9]

(Synthesis of polysiloxane a-9)

(A-9, 40) was obtained in the same manner as the polysiloxane a-8 except that anhydrous hyalic acid was changed to cis-4-cyclohexene-1,2-dicarboxylic acid anhydride Viscosity of 80 Poise) was obtained. When the ESR of the polysiloxane (a-9) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.51 x 10 < ^-6 > mol / g.

[Synthesis Example 10]

(Synthesis of polysiloxane a-10)

Polysiloxane (a-10, viscosity at 40 캜 was 70 Poise) was obtained in the same manner as polysiloxane a-8, except that anhydrous hymic acid was changed to itaconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). When the ESR of the polysiloxane (a-10) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.52 x 10 < ^-6 > mol / g.

[Synthesis Example 11]

(Synthesis of polysiloxane a-11)

A 1 L eggplant-shaped flask was charged with a stirrer, 0.60 mol (173.14 g) of (3-trimethoxypropyl) succinic anhydride, 4-hydroxy-TEMPO (trade name: X-12-967C, manufactured by Shin- 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.00 mmol (0.83 mmol) of Ba (OH) ₂ .H ₂ O powder g) (manufactured by SIGMA-ALDRICH), and 0.58 mol (20.30 g) of methanol were charged and stirred using a magnetic stirrer. Dimros was attached and the temperature was raised from room temperature to 75 캜 by using an oil bath and refluxed for 2.5 hours to open anhydrous succinic acid.

2.40 mol (432.52 g) of DPD (diphenylsilanediol) (Shin-Etsu Chemical Co., Ltd.) and 1.40 mol (347.69 g) of MEMO (3-methacryloxypropyltrimethoxysilane) were placed in a 2 L separable flask, The whole amount of the prepared (3-trimethoxypropyl) succinic anhydride was introduced, and the mixture was stirred using a stirring blade and a three-one motor. And the temperature was raised from room temperature to 95 캜 using an oil bath. After 1 hour, the heating was continued, and the dim rods were removed and connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump to remove methanol. Heating was continued for 10 hours while the vacuum state was maintained, and then the pressure was returned to the atmospheric pressure, and the solution was cooled to room temperature to obtain a transparent polysiloxane (a-11, viscosity at 40 DEG C of 84 Poise). When the ESR of the polysiloxane (a-11) was measured, a peak of g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.50 x 10 < ^-6 > mol / g.

(Preparation of polysiloxane composition)

[Example 1]

46.57 g of the polysiloxane (a-1) obtained in Synthesis Example 1, 0.79 g of IRGACURE 819 (BASF), and 0.01 g of 4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) (Except for the diluting solvent), KBM5103 (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), 37.26 g of TINUVIN 405 (BASF), EA- (3-acryloxypropyltrimethoxysilane), 0.23 g of TINUVIN 152 (manufactured by BASF) and 28.87 g of PGMEA (propylene glycol monomethyl ether acetate), and the mixture was stirred with a web rotor. This was subjected to pressure filtration with a PP-made filter having a pore diameter of 2.5 microns to obtain a polysiloxane composition.

[Examples 2 to 27 and Comparative Examples 1 to 5]

Examples 2 to 27 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the components shown in the following Tables 1, 2 and 3 were used in the ratios shown in the same Tables, Or a resin composition.

With respect to the polysiloxane compositions of Examples 1 to 27 and the resin compositions of Comparative Examples 1 to 5, the Amplitude was set to 200, and the ESR was measured.

In the polysiloxane compositions of Examples 1 to 8 and 12 to 27 and the resin composition of Comparative Example 5, a peak having a g value of 2.007 as shown in Fig. 4 was observed.

In the polysiloxane composition of Example 9, a peak having a g value of 2.007 as shown in Fig. 5 was observed.

In the polysiloxane composition of Example 10, a peak having a g value of 2.007 as shown in Fig. 6 was observed.

In the polysiloxane composition of Example 11, a peak of g value of 2.007 as shown in Fig. 7 was observed.

In the polysiloxane composition of Example 12, a peak having a g value of 2.007 as shown in Fig. 8 was observed.

In the resin compositions of Comparative Examples 1 to 3, as shown in Fig. 9, peaks were observed in the range of g value of 2.034 to 1.984, but the radical concentration was out of the range of the claims.

In the resin composition of Comparative Example 4, as shown in Fig. 10, a peak with a g value of 2.007 was observed.

The results of the above evaluations of the polysiloxane compositions of Examples 1 to 27 and the resin compositions of Comparative Examples 1 to 5 are shown in Tables 1, 2 and 3 below.

&Lt; Component (B) >

Irgacure 819: manufactured by BASF

&Lt; Component (C) >

c-1: The following formula:

4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.)

c-2: The following formula:

(Manufactured by TOKYO KASEI Co., Ltd.)

c-3:

4-oxo-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.)

c-4:

3-carboxy-proxyl-free radical (manufactured by Tokyo Chemical Industry Co., Ltd.)

&Lt; Component (D) >

EA-1020: manufactured by Shin Nakamura Kakugo Co., Ltd.

A600: manufactured by Shin Nakamura Kakugo Co., Ltd.

&Lt; Component (E) >

TINUVIN405: manufactured by BASF

&Lt; Component (F) >

EA-6340: Shin-Nakamura Kagaku Co., Ltd. Acid value: 85 mgKOH / g

SPC1001: manufactured by Showa Denko K. acid value: 86 mgKOH / g

&Lt; Component (G) >

KBM5103: manufactured by Shin-Etsu Kakugo Co., Ltd.

&Lt; Component (H) >

TINUVIN152: manufactured by BASF

&Lt; Component (I) >

PEGMEA: Tokyo is a taxi teacher manufacturing

The crack resistance in Examples 1 to 27 was evaluated using a silicon wafer of Mo sputtering. In Examples 1 to 20 and Examples 24 to 27, no peeling occurred in the pattern and cracks were not generated. However, In Examples 21 to 23, peeling occurred in the patterns.

In Comparative Example 5, when exposed and developed, the film could not be evaluated because no film remained.

The polysiloxane composition having an alkali-soluble group of the present invention is used as an insulating material of a display device in the formation of a surface protective film, an interlayer insulating film, an? Ray shielding film and the like in a semiconductor device and an image sensor, a micromachine or a microactuator Semiconductor devices, and the like, and the formation thereof.

Claims

The sample was allowed to stand for 24 hours in a dark atmosphere at 24 ° C, atmospheric pressure, and light of a wavelength of 400 nm or less. Thereafter, a peak having a g value of 2.034 to 1.984 was measured with an electron spin resonance (ESR) By weight, based on 1 g of the solid content in the composition, of 0.1 x 10 < ^-6 > to 120 x 10 < ^-6 > moles of radicals.

The polysiloxane composition of claim 1 having a radical crosslinkable group having the structure:

3. The polysiloxane composition according to claim 1 or 2, further having an alkali-soluble group, the radical-crosslinkable group having a radical-crosslinkable group.

(B) a photoradical initiator.

The positive resist composition according to claim 4, wherein the polysiloxane composition comprises (A) a polysiloxane having a radical crosslinkable group (A) in an amount of 1 part by mass to 99 parts by mass, (B) a photo radical initiator in an amount of 0.01 part by mass to 15 parts by mass based on 100 parts by mass of the total solid content in the polysiloxane composition; And 0.005 parts by mass to 2 parts by mass of (C) a nitroxy compound.

The polysiloxane composition of claim 5, wherein the (C) nitroxy compound is represented by the formula:

7. The polysiloxane composition according to any one of claims 1 to 6, wherein the (A) polysiloxane having a radical crosslinkable group is a polysiloxane having a (meth) acryloyl group and / or a styryl group.

8. The polysiloxane composition according to any one of claims 1 to 7, further comprising (D) a compound having a photopolymerizable double bond in an amount of 5 parts by mass to 45 parts by mass based on 100 parts by mass of the total solid content in the polysiloxane composition.

9. The polysiloxane composition according to any one of claims 1 to 8, further comprising 0.01 to 10 parts by mass of (E) an ultraviolet absorber based on 100 parts by mass of the total solid content in the polysiloxane composition.

The positive resist composition according to any one of claims 1 to 9, further comprising 1 to 50 parts by mass of (F) an alkali-soluble resin having an acid value of 10 to 200 mgKOH / g based on 100 parts by mass of the total solid content in the polysiloxane composition &Lt; / RTI >

11. The polysiloxane composition according to any one of claims 1 to 10, wherein the (A) polysiloxane having a radical crosslinkable group has a structure represented by the following formula.

Wherein Ph represents a phenyl group.

A cured product obtained by curing the polysiloxane composition according to any one of claims 1 to 11.

A transparent insulating film obtained by curing the polysiloxane composition according to any one of claims 1 to 11.