KR20220136129A - Composition for adhesive layer, layered product, and producing and processing method of the layered product using the composition - Google Patents

Abstract

The purpose of the present invention is to provide a composition for forming an adhesive layer which is easily peelable from an adherend by laser irradiation at 355 nm and also has good adhesion to the adhesive layer of the adherend and good solvent resistance. The present invention relates to a composition for forming an adhesive layer to form an adhesive layer capable of adhering a support and an adherend and also separating the support and the adherend by being irradiated with light. The composition comprises: (A) a polymerizable compound containing an unsaturated group, (B) an ultraviolet absorber, and (F) a solvent, wherein the content of (B) the ultraviolet absorber is 10 mass % or more and 80 mass % or less with respect to the total mass of solid content.

Description

A composition for forming an adhesive layer, a laminate, a method for manufacturing a laminate, and a method for processing a laminate

The present invention relates to a composition for forming an adhesive layer, a laminate, a method for manufacturing the laminate, and a method for processing the laminate.

(Background art regarding the first disclosure)

BACKGROUND ART In recent years, thickness reduction of mounted flexible displays and semiconductor chips, etc. is progressing in accordance with high functionalization of digital devices and the like. However, it is difficult to convey the flexible display, the semiconductor chip, etc. whose intensity|strength fell by thickness reduction by the conventional automatic conveyance.

Then, the method for safely and easily conveying a thinned flexible display, a semiconductor chip, etc. is examined. For example, a method of creating a laminate in which an adherend such as a flexible display and a semiconductor chip is fixed through an adhesive layer on a light-transmitting support such as a glass substrate, and conveying the flexible display and semiconductor chip, etc. for each laminate is being reviewed. At this time, as the adhesive layer, there is a case in which a composition in which the adhesive strength is reduced due to deterioration or decomposition when irradiated with light is used. When the adhesive layer is used, by irradiating light from the support side toward the adhesive layer after transport, the adherend can be separated (peeled) from the support and transferred, for example, to another substrate (laser lift-off process, hereinafter, Also called "LLO process").

As a composition for an adhesive agent enabling the LLO process, Patent Document 1 describes a composition in which a curable resin having a 9,9'-diphenylfluorene (cardo) structure and an unsaturated group is dissolved in a solvent. Patent Document 1 describes that the adhesive layer formed by applying this composition on a glass support and heating it can easily peel the glass support from the adherend by irradiation with a laser having a wavelength of 308 nm. In Patent Document 1, a composition obtained by dissolving a resin having a benzotriazole structure in a solvent is applied on a glass support, and the adhesive layer formed by heating is irradiated with a laser having a wavelength of 355 nm to easily remove the glass support from the adherend. It is described that it was able to peel easily.

Moreover, in patent document 2, the photosensitive composition which has a curable resin containing a cardo structure and an unsaturated group, a photopolymerizable monomer, and a light absorber (carbon black) is described as said composition for adhesive agents. Patent document 2 describes that this photosensitive composition was excellent in the adhesiveness to the to-be-adhered body of the cured film which apply|coated on the glass support body, and was heated and formed.

(Background art regarding the second disclosure)

In addition, a solid-state image sensor such as a charge coupled device (CCD) image sensor or a complementary metal-oxide semiconductor (CMOS) image sensor is mounted on an image pickup device such as a digital camera or a cellular phone equipped with a camera. The image sensor has a fine condensing lens (microlens) for the purpose of improving the light condensing rate. In recent years, high pixelation, high sensitivity, and miniaturization of the image sensor are required, and development of materials for microlenses capable of responding to them is being conducted.

For example, Patent Document 3 discloses a resin composition used for forming a microlens pattern, including an alkali-soluble resin having a glass transition temperature (Tg) of 70° C. or less, and a photosensitizer. According to patent document 3, it is said that the said resin composition can form a fine dot pattern also by the heat flow of low temperature (60-100 degreeC). Patent Document 3 describes that the resin composition can form a microlens pattern by forming a positive pattern that removes an exposed portion.

Further, Patent Document 4 discloses a siloxane resin composition containing a siloxane resin, metal-containing particles, and a polymerizable compound having an ethylenically unsaturated double bond. According to patent document 4, the said siloxane resin composition makes the ratio of Ti and Zr contained in the metal-containing particle|grains into a specific range, maintaining the high refractive index of the hardened|cured material of a siloxane resin composition, It is said that light resistance can be improved more. Patent document 4 describes that the said siloxane resin composition can form a microlens pattern by negative pattern formation which removes an unexposed part.

Japanese Patent Laid-Open No. 2012-106486 Japanese Patent Laid-Open No. 2018-001604 Japanese Patent Laid-Open No. 2020-100793 Japanese Patent Laid-Open No. 2019-173016

(1st assignment)

Conventionally, the development of an adhesive used in the LLO process has been focused on a composition capable of peeling off an adherend by a short-wavelength laser (wavelengths 248 nm and 266 nm, etc.) having high energy and excellent processability. However, in order to process with the laser of these wavelengths, it is necessary to use the support body which consists of expensive materials, such as quartz glass and a sapphire substrate with high transmittance in a short wavelength region. Therefore, the conventional LLO process has a problem that the running cost becomes high. Then, in order to use a cheaper transparent glass, development of the adhesive bond layer which can peel off the to-be-adhered body by a longer wavelength laser (for example, 355 nm etc.) is calculated|required.

However, the conventionally known adhesive composition has a high transmittance at 355 nm, and it is difficult to peel the adherend by laser irradiation. In addition, Patent Document 1 describes a composition capable of peeling an adherend by irradiation with a laser of 355 nm. However, according to the knowledge of the present inventors, this composition has a low adhesive strength of the adherend to the adhesive layer, or of a cured film. I have a problem that the solvent resistance is low or not.

The invention according to the first disclosure in the present specification has been made in view of such a point, and an adhesive that is easy to peel off an adherend by laser irradiation at 355 nm, and has good adhesion and solvent resistance to the adhesive layer of the adherend. An object of the present invention is to provide a composition for forming a layer, a laminate formed by bonding a support and an adherend to each other using the composition for forming an adhesive layer, and a method for manufacturing and processing the laminate.

One aspect of the present invention for solving the problems related to the first disclosure is an adhesive layer for bonding a support and an adherend, and forming an adhesive layer that enables separation of the support and the adherend by being irradiated with light. It relates to a composition for forming. The composition contains (A) an unsaturated group-containing polymerizable compound, (B) an ultraviolet absorber, and (F) a solvent, and the content of the (B) ultraviolet absorber is 10% by mass or more and 80% by mass based on the total mass of the solid content. % or less.

Another aspect of the present invention for solving the problems related to the first disclosure is an adhesive layer comprising a support, an adherend, and a cured product of the composition for forming an adhesive layer disposed between the support and the adherend. It relates to a laminate having

Another aspect of the present invention for solving the problems related to the first disclosure is a step of forming an adhesive layer by applying the composition for forming an adhesive layer to at least one surface of a support and an adherend, and the formed adhesive It relates to a manufacturing method of a laminate including a step of adhering the support and the adherend through a layer.

Another aspect of the present invention for solving the problems related to the first disclosure is a laminate comprising a step of preparing the laminate and a step of separating the support and the adherend by irradiating the adhesive layer with light. of the processing method.

Another aspect of the present invention for solving the problem of the second disclosure relates to a solid-state imaging device including the microlens.

Another aspect of the present invention for solving the problem of the second disclosure relates to an imaging device including the solid-state imaging device.

According to the invention according to the first disclosure in the present specification, a composition for forming an adhesive layer that is easy to peel off an adherend by laser irradiation of 355 nm, and has good adhesion and solvent resistance of the adherend to the adhesive layer, Provided are a laminate formed by bonding a support and an adherend to each other using a composition for forming an adhesive layer, and a method for manufacturing and processing the laminate.

According to the invention according to the second disclosure in the present specification, there is little limitation of the resin that can be used, and a composition for forming a microlens that hardly produces a residue during development, a method for producing a microlens using the composition, and the composition The cured film formed by hardening|curing, the solid-state imaging element provided with the said microlens, and the imaging device which has the said solid-state imaging element can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment. In addition, in this invention, when the 1st decimal place is 0 about content of each component, the description below a decimal point may be abbreviate|omitted. In addition, as for the compound, functional group, or structure illustrated after this, unless there is particular notice, only 1 type may be used in what was illustrated, and multiple types may be used together.

The first indication in this specification for solving the said 1st subject is,

(A) an unsaturated group-containing polymerizable compound;

(B) an ultraviolet absorber;

(F) a solvent;

including,

(B) Content of a ultraviolet absorber relates to the composition for curable adhesive bond layer formation which is 10 mass % or more and 80 mass % or less with respect to the total mass of solid content.

In addition, the 2nd indication in this specification for solving the 2nd problem mentioned later is,

(A1) an unsaturated group-containing polymerizable compound which is an alkali-soluble resin;

(A2) an unsaturated group-containing polymerizable compound having no alkali-soluble group;

(B) an ultraviolet absorber;

(C) an epoxy compound having two or more epoxy groups;

(D) a photoinitiator;

(F) comprising a solvent;

(B) Content of a ultraviolet absorber relates to the composition for microlens formation which are 3 mass % or more and 20 mass % or less with respect to the total mass of solid content.

Since the materials used for these compositions are common, the materials to be used are first described, and then, preferred forms of the respective compositions using the materials are described.

1. Material

1-1. (A) unsaturated group-containing polymerizable compound

(A) An unsaturated group-containing polymerizable compound (hereinafter, simply referred to as “component (A)”) is a compound having a polymerizable unsaturated group and curing the polymerizable unsaturated group by generating a polymerization reaction by stimulation such as heat and light. .

(A) component improves the adhesiveness to the to-be-adhered body or base material of the cured film formed by hardening|curing each composition, and solvent resistance.

The component (A) should just be what can ensure the adhesiveness to a to-be-adhered body or a base material, and solvent resistance, and it can be set as well-known unsaturated group containing polymeric compounds, such as alkali-soluble resin and an acrylic resin.

(A) Component is roughly divided into (A1) component which is alkali-soluble resin, and (A2) component which is another unsaturated group containing polymeric compound which does not have an alkali-soluble group.

(A1) It is preferable that the alkali-soluble resin as a component has a polymerizable unsaturated group (preferably (meth)acryloyl group) and an acidic group (alkali-soluble group) for expressing alkali solubility in one molecule, It is more preferable to contain both a polymerizable unsaturated group and a carboxy group. If it is the said resin, it can use widely, without a case specifically limited. Since the said alkali-soluble resin has a polymerizable unsaturated group and a carboxy group together, when patterning of each composition is required, in addition to providing outstanding photocurability, it provides favorable developability and patterning property.

Alkali-soluble resin as component (A1) according to the present embodiment is a polymerizable unsaturated group-containing alkali obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups and (meth)acrylic acid with a polybasic acid carboxylic acid or anhydride thereof. It is preferable that it is a soluble resin. In the production of the alkali-soluble resin, a polyester is produced by reaction of a hydroxyl group with a polybasic carboxylic acid, but the average degree of polymerization is preferably a low molecular weight of about 2 to 500. In addition, "(meth)acrylic acid" is a generic name of acrylic acid and methacrylic acid, "(meth)acryloyl group" is a generic name of an acryloyl group and a methacryloyl group, and means one or both of these.

It is preferable that the said epoxy compound is an epoxy compound which has two or more epoxy groups. Examples of such an epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a phenol novolak type epoxy compound, and a cresol novolak type epoxy compound (e.g., EPPN-501H: Nippon Chemicals) Co., Ltd.), a phenol aralkyl type epoxy compound, a phenol novolac compound containing a naphthalene skeleton (eg, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), a biphenyl type epoxy compound (eg, jER YX4000: Samreung Chemical Co., Ltd.) production), naphthol aralkyl type epoxy compound, trisphenolmethane type epoxy compound, tetrakisphenol ethane type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polyhydric carboxylic acid, methacrylic acid and glycidyl methacrylate A copolymer of a monomer having a (meth)acrylic group containing (meth)acrylic acid glycidyl as a unit represented by a copolymer of dill, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (For example, Celoxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (eg, Epolide GT401: manufactured by Daicel Corporation) , an epoxy compound having an epoxycyclohexyl group typified by HiREM-1 manufactured by Sakkuk Hwasung Industrial Co., Ltd., a polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series: manufactured by DIC Corporation), 2,2- 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g. , NISSO-PB·JP-100: manufactured by Nippon Procurement Co., Ltd.) and an epoxy compound having a silicone skeleton, and the like.

(A1) As alkali-soluble resin which is a component, an acrylic copolymer is also used preferably.

Resin which is copolymers, such as (meth)acrylic acid and (meth)acrylic acid ester, and has a (meth)acryloyl group and a carboxy group is contained in the example of an acrylic copolymer. In an example of the resin, (meth)acrylic acid is reacted with a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, and finally dicarboxylic acid or tricarboxylic acid Polymeric unsaturated group containing alkali-soluble resin obtained by making the anhydride of an acid react is contained. The copolymer has 20 to 90 mol% of repeating units derived from diester glycerol esterified with (meth)acrylic acid with hydroxyl groups at both ends, as disclosed in Japanese Patent Application Laid-Open No. 2014-111722, and at least one type of polymerization copolymerizable therewith. It is composed of 10 to 80 mol% of repeating units derived from a sexually unsaturated compound, and a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH/g, as shown in Japanese Patent Application Laid-Open No. 2018-141968 A unit derived from a (meth)acrylic acid ester compound and a unit having a (meth)acryloyl group and a di or tricarboxylic acid residue, the weight average molecular weight (Mw) 3000-50000, acid value 30-200 mg A polymerizable unsaturated group-containing alkali-soluble resin which is a polymer of KOH can be referred to.

From the viewpoint of further improving the heat resistance, solvent resistance, and adhesion to the adherend or substrate of the cured film, the component (A1) preferably has a plurality of aromatic rings and is an alkali-soluble resin having a repeating unit containing a fluorene structure. It is more preferable that it is alkali-soluble resin which has a repeating unit containing the bisarylfluorene skeleton. For example, it is preferable that (A1) component is resin represented by following General formula (1).

In formula (1), Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and some of the hydrogen atoms constituting Ar are an alkyl group having 1 or more and 10 or less carbon atoms, 6 or more and 10 or less carbon atoms. may be substituted with an aryl group or arylalkyl group, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number 0 or more and 3 or less. G is independently a (meth)acryloyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number with an average value of 1 or more and 20 or less.

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is saturated having 2 or more and 20 or less carbon atoms. or an unsaturated hydrocarbon group, and p is a number of 0 or more and 10 or less.

In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is the number of 1 or 2.

Resin represented by General formula (1) can be synthesize|combined with the following method.

First, an epoxy compound (a-1) having a bisarylfluorene skeleton which may have several alkylene oxide modified groups in one molecule represented by the following general formula (5) (hereinafter only “epoxy compound (a-1)” "), (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6), and a (meth)acrylic acid derivative represented by the following general formula (7) are reacted, The diol compound which is (meth)acrylate is obtained. Further, the bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

In formula (5), each Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and a part of the hydrogen atoms constituting Ar is an alkyl group having 1 or more and 10 or less carbon atoms, 6 or more and 10 carbon atoms. It may be substituted with the following aryl group or arylalkyl group, a C3-C10 cycloalkyl group or a cycloalkylalkyl group, a C1-C5 alkoxy group, or a halogen group. R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number 0 or more and 3 or less.

In formulas (6) and (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, and R ₄ is saturated having 2 to 20 carbon atoms. or an unsaturated hydrocarbon group, and p is a number of 0 or more and 10 or less.

A well-known method can be used for the reaction of the said epoxy compound (a-1) and (meth)acrylic acid or its derivative(s). For example, in Japanese Unexamined Patent Publication No. 4-355450, by using about 2 moles of (meth)acrylic acid with respect to 1 mole of the epoxy compound having two epoxy groups, a diol compound containing a polymerizable unsaturated group is obtained. is described. In the present embodiment, the compound obtained in the above reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (8) (hereinafter also referred to simply as “diol (d)”).

In the formula (8), each Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and a part of the hydrogen atoms constituting Ar is an alkyl group having 1 or more and 10 or less carbon atoms, 6 or more and 10 carbon atoms. It may be substituted with the following aryl group or arylalkyl group, a C3-C10 cycloalkyl group or a cycloalkylalkyl group, a C1-C5 alkoxy group, or a halogen group. G is each independently a (meth)acryloyl group, a substituent represented by General Formula (2) or General Formula (3), and R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number 0 or more and 3 or less.

In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is saturated having 2 or more and 20 or less carbon atoms. or an unsaturated hydrocarbon group, and p is a number of 0 or more and 10 or less.

Next, the obtained diol (d), dicarboxylic acid or tricarboxylic acid or its acid monhydride (b), and tetracarboxylic acid or its acid dianhydride (c) are reacted, and the general formula (1) ), it is possible to obtain an unsaturated group-containing curable resin having a carboxyl group and a polymerizable unsaturated group in one molecule.

The acid component is a polyvalent acid component capable of reacting with a hydroxyl group in the diol (d) molecule. In order to obtain resin represented by General formula (1), it is necessary to use together dicarboxylic acid or tricarboxylic acid, or those acid monohydride (b), and tetracarboxylic acid or its acid dianhydride (c). . The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Moreover, in these carboxylic acid residues, the bond containing hetero elements, such as -O-, -S-, and a carbonyl group, may be contained.

Examples of the dicarboxylic acid or tricarboxylic acid, or their acid monohydride (b) include a chain hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbondicarboxylic acids or tricarboxylic acids, and acid monohydrides thereof, and the like.

Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and their dicarboxylic acids or tricarboxylic acids into which optional substituents have been introduced, and the like.

Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid. , chlorendic acid, hexahydrotrimellitic acid and norbornanedicarboxylic acid and the like, and their dicarboxylic acids or tricarboxylic acids into which optional substituents are introduced.

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and trimellitic acid, and optional substituents These dicarboxylic acids or tricarboxylic acids into which have been introduced are included.

Among these dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. do.

As the dicarboxylic acid or tricarboxylic acid, it is preferable to use the acid monoanhydride.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and acid dianhydrides thereof.

Examples of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and these chain hydrocarbons introduced with substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups. tetracarboxylic acid and the like.

Examples of the alicyclic hydrocarbontetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid and norbornanetetracarboxylic acid, and chain and these alicyclic tetracarboxylic acids into which substituents such as a formula hydrocarbon group and an unsaturated hydrocarbon group have been introduced are included.

Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and naphthalene-1,4 ,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid, and the like.

Among these tetracarboxylic acids, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferable, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferable. .

It is preferable to use the acid dianhydride as said tetracarboxylic acid.

Further, in place of the tetracarboxylic acid or its acid dianhydride (c), bis-anhydride trimellitic acid aryl esters may be used. The bis-anhydride trimellitic acid aryl esters are, for example, compounds produced by the method described in International Publication No. 2010/074065, and structurally include two aromatic diols (naphthalenediol, biphenol, and terphenyldiol). It is an acid dianhydride of the type in which a hydroxyl group and the carboxyl group of two molecules of trimellitic anhydride are respectively reacted to form an ester bond.

The reaction method of the diol (d) with the acid components (b) and (c) is not particularly limited, and a known method can be employed. For example, Japanese Patent Laid-Open No. 9-325494 describes a method in which epoxy (meth)acrylate and tetracarboxylic dianhydride are reacted at a reaction temperature of 90 to 140°C.

At this time, epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid, or their acid monohydride (b) and tetracarboxylic dianhydride (c) so that the terminal of the compound becomes a carboxyl group It is preferable to react so that the molar ratio of (d):(b):(c)=1.0:0.01 to 1.0:0.2 to 1.0.

For example, in the case of using the acid monohydride (b) and the acid dianhydride (c), the molar ratio [[(b)] of the amount of the acid component to the diol (d) [(b)/2+(c)] )/2+(c)]/(d)] is preferably greater than 0.5 and less than or equal to 1.0. When the molar ratio is 1.0 or less, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) does not become an acid anhydride, so it is possible to suppress an increase in the content of unreacted acid dianhydride and improve the stability over time of each composition. . In addition, when the molar ratio is greater than 0.5, it is possible to suppress an increase in the residual amount of unreacted components in the diol (d) containing a polymerizable unsaturated group, thereby improving the stability over time of each composition. In addition, for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (1), the molar ratio of each component of (b), (c) and (d) can be arbitrarily changed within the above range. have.

In addition, the synthesis|combination of diol (d) and reaction of polyhydric carboxylic acid or its anhydride following it are normally performed using a catalyst as needed in a solvent.

Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, and high boiling point ethers such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate. and ketone solvents such as cyclohexanone and diisobutyl ketone and ester solvents. In addition, reaction conditions, such as a solvent used and a catalyst, are although it does not restrict|limit especially, For example, it is preferable to use as a reaction solvent the solvent which does not have a hydroxyl group and has a boiling point higher than the reaction temperature.

In addition, it is preferable to perform reaction of an epoxy group, a carboxy group, or a hydroxyl group using a catalyst. As the catalyst, Japanese Patent Laid-Open No. 9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine. etc. are described.

It is preferable that acid values are 50 mgKOH/g or more and 200 mgKOH/g, and, as for unsaturated group containing curable resin represented by General formula (1), it is more preferable that they are 60 mgKOH/g or more and 150 mgKOH/g or less. When the acid value is 50 mgKOH/g or more, it becomes difficult to leave a residue at the time of alkali development, and when it is 200 mgKOH/g or less, the penetration of the alkali developer does not become excessively rapid, so the peeling phenomenon can be suppressed. In addition, the acid value can be calculated|required by titrating with 1/10N-KOH aqueous solution using the potentiometric titration apparatus "COM-1600" (made by Pyeongsang Industrial Co., Ltd.).

(A1) The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) measurement (HLC-8220GPC, manufactured by Tosoh Corporation) of the alkali-soluble resin of the component is preferably 1000 or more and 40000 or less, and 1500 or more 30000 It is more preferable that they are below, and it is more preferable that they are 2000 or more and 15000 or less. The adhesiveness of a support body and to-be-adhered body can be improved as a weight average molecular weight (Mw) is 1000 or more. In addition, if the weight average molecular weight (Mw) is 40000 or less, it is easy to adjust the solution viscosity of the composition suitable for application, and the application to the surface of the support or adherend does not require too much time, and the adhesiveness to the adherend is not more likely to rise When attaching importance to adhesive strength, it is preferable that weight average molecular weights (Mw) are 1000 or more and 4500 or less.

(A2) The other unsaturated group-containing polymerizable compound as a component (hereinafter, simply referred to as "component (A2)") has two or more polymerizable unsaturated groups, and an alkali that generates a polymerization reaction by stimulation such as heat and light. It is a compound which does not have a soluble group.

(A2) In addition to improving the adhesive strength and solvent resistance to the to-be-adhered body or base material of the cured film formed by hardening|curing each composition, a component can make exposure sensitivity and developability favorable. The component (A2) may have at least two or more polymerizable unsaturated groups capable of reacting (polymerizing) with the polymerizable unsaturated group of the component (A1) or the polymerizable unsaturated group of the molecule of the other component (A2). When the said polymerizable unsaturated group uses together with (A1) component, it is preferable that it is the same functional group as the polymerizable unsaturated group which (A1) component has. Specifically, it is preferable that the said polymerizable unsaturated group is a (meth)acryloyl group. In addition, a monomer may be sufficient as (A2) component, and an oligomer and a polymer may be sufficient as it. When using together with (A1) component, it is preferable that (A2) component is a monomer or an oligomer.

(A2) In the example of a component,

(meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol Ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (meth)acrylic acid esters of meth)acrylate and dipentaerythritol hexa(meth)acrylate;

Urethane such as pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer acrylate monomers;

Bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, bisphenol fluorene epoxy (meth) acrylate, diphenyl fluorene epoxy (meth) acrylate, phenol novolac epoxy (meth) Epoxy (meth)acrylates, such as an acrylate, cresol novolak-type epoxy (meth)acrylate, and a phenol aralkyl-type epoxy (meth)acrylate; and

As a compound which has an ethylenic double bond, the dendritic polymer etc. which have a (meth)acryl group are contained.

(A2) It is preferable to have a 2 or more (meth)acryloyl group, and, as for a component, it is more preferable to have a 3 or more (meth)acryloyl group. When the said (A2) component has two or more (meth)acryloyl groups, a crosslinking density improves and the solvent resistance of a cured film improves.

1-2. (B) UV absorber

[(B) component]

(B) Component is a ultraviolet absorber.

In addition, in this specification, the ultraviolet absorber means the compound which has a clear absorption peak in an ultraviolet region, specifically, an organic compound. Carbon black etc. which show broad absorption are not contained in the ultraviolet absorber in this specification. Since the ultraviolet absorber does not absorb light in the visible region, it is difficult to generate a colored residue. Moreover, the said ultraviolet absorber is easy to melt|dissolve in an alkali stripping solution, and washing|cleaning after peeling is easy.

(B) component is 250 nm or more and 450 nm or less, It is good just to be a compound which preferably has an absorption peak between the wavelengths of 300 nm or more and 450 nm.

(B) Examples of the component include a benzotriazole structure, a benzophenone structure, a triazine structure, a salicylic acid structure, a benzoate structure, a cinnamic acid derivative structure, a naphthalene derivative structure, a structure based on anthracene and its derivatives, and a dinaphthalene structure. Compounds having a structure having a structure and a phenanthrolyline structure and the like are included. Among these, the compound which has a benzotriazole structure, a benzophenone structure, and a triazine structure from the point which absorbs the ultraviolet-ray of 355 nm efficiently is preferable.

Examples of the compound having a benzotriazole structure include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5'- di-t-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-{2'-hydroxy-3'-(3",4", 5",6"-tetrahydrophthalimidemethyl)-5'-methylphenyl}benzotriazole, C7-C9-alkyl-3-[3-(2H-benzotriazol-2-yl)-5-(1) ,1-dimethylethyl)-4-hydroxyphenyl]propionether and the like.

Examples of the compound having a benzophenone structure include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy -4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone , 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, hydroxydodecylbenzophenone and the like are included. .

Examples of the compound having a triazine structure include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine, 2 -[4((2-hydroxy-3-dodecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine , 2-[4-((2-hydroxy-3-tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. are included.

1-3. (C) an epoxy compound having two or more epoxy groups

(C) The epoxy compound which has two or more epoxy groups forms a sufficient crosslinked structure, and improves the chemical-resistance of a cured film.

(C) In the example of a component, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a bisnaphthofluorene type epoxy compound, a diphenylfluorene type epoxy compound, a phenol novolak type epoxy compound , cresol novolak type epoxy compound, phenol aralkyl type epoxy compound, phenol novolak compound containing naphthalene skeleton (eg NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compound (eg jER YX4000: Samreung) Manufactured by Chemical Corporation, "jER" is a registered trademark of the company), naphthol aralkyl type epoxy compound, trisphenol methane type epoxy compound (e.g. EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenol ethane type epoxy compound, polyhydric alcohol A monomer having a (meth)acrylic group comprising (meth)acrylic acid glycidyl represented by a glycidyl ether of of copolymer, 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021P: manufactured by Dai Cell Co., Ltd., "Celoxide" is a registered trademark of the company), butane Tetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., Epolide GT401: manufactured by Daicel Co., Ltd., “Epolide” is a registered trademark of the company), an epoxycyclohexyl group Epoxy compound having (for example, HiREM-1: manufactured by Sakuk Chemical Industry Co., Ltd.), a polyfunctional epoxy compound having a dicyclopentadiene skeleton (eg, HP7200 series: manufactured by DIC Corporation), 2,2-bis(hydroxymethyl) ) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of -1-butanol (eg, EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (eg, NISSO-PB JP) -100: manufactured by Nippon Procurement Co., Ltd., "NISSO-PB" is a registered trademark of the company), an epoxy compound having a silicone skeleton, and the like. In addition, these compounds may use only 1 type of compound and may use 2 or more types together.

(C) In component, bisphenol A epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, bisnaphthofluorene type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, bi It is preferable that it is a phenyl type epoxy compound, and it is more preferable that it is a biphenyl type epoxy compound. By using a biphenyl-type epoxy compound, the mechanical strength and chemical resistance of the cured product according to the required characteristics and the patterning property of the composition for forming microlenses during photocuring can be achieved, and the composition for forming microlenses is designed The degree of freedom can be increased.

(C) It is preferable that they are 100 g/eq or more and 300 g/eq or less, and, as for the epoxy equivalent of the epoxy compound of component, it is more preferable that they are 100 g/eq or more and 250 g/eq or less. Moreover, it is preferable that the number average molecular weights (Mn) of the epoxy compound of (C)component are 100 or more and 5000 or less. If the epoxy equivalent is 100 g/eq or more and the epoxy compound number average molecular weight (Mn) is 100 or more, a cured film having good solvent resistance may be obtained, the epoxy equivalent is 300 g/eq or less, and the number average molecular weight (Mn) is 5000 If it is below, sufficient alkali resistance can be maintained even when using an alkaline chemical solution in a post process.

In addition, the epoxy equivalent of the epoxy compound of (C) component can be calculated|required by titrating with 1/10N-perchloric acid solution using the potentiometric titration apparatus "COM-1600" (made by Pyeongsang Industrial Co., Ltd.). In addition, the said epoxy compound number average molecular weight (Mn) can be calculated|required by the above-mentioned gel permeation chromatography (GPC) "HLC-8220GPC" (made by Tosoh Corporation), for example.

(C) When using a component, you may use a hardening|curing agent and a hardening accelerator together.

Examples of the curing agent include an amine compound, a polyhydric carboxylic acid compound, a phenol resin, an amino resin, a dicyandiamide, and a Lewis acid complex compound.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc. do. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and a hindered phenol-based compound. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fibers, silica, mica and alumina and the like. Examples of the antifoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-ureidopropyltriethoxy silane and the like.

1-4. (D) photoinitiator

(D) A photoinitiator can fully advance reaction of the part irradiated with light, can reduce the solubility of the hardened|cured part at the time of image development, and can form a desired fine pattern.

(D) Examples of the component include 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2 -(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-me Toxyphenyl) -4,5-diphenyl biimidazole, 2,4,5-triarylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra biimidazole-based compounds such as phenyl-1,2-biimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloro halomethylthiazole compounds such as romethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5- Trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1 , halomethyl-s-triazine-based compounds such as 3,5-triazine; 1,2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (Ilgacure OXE01, manufactured by BASF Japan, “Ilgacure” is a registered trademark of the company), 1 -(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O- Acetate, 1-(4-methylsulfanylphenyl)butan-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bi Cycloheptyl-1-oneoxime-O-acetate, 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-oneoxime-O- Benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-Thiophenylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-oneoxime -O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-benzoate, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-ethan-1-oneoxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-Ethan-1-oneoxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-oneoxime -O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione=2-O-benzoyloxime, 1-[9-ethyl-6-(2-methyl) Benzoyl) carbazol-3-yl] ethanone-O-acetyloxime, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, One- [7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), ethanone, 1-(-9,9-dibutyl- 7-Nitro-9H-fluoren-2-yl)-1-O-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- , 1-(O-acetyloxime) (Ilgacure OXE02) O-acyloxime compounds; benzyl dimethyl ketal; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; and organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide. In addition, these photoinitiators may be used individually by 1 type, and may use 2 or more types together.

Among these, as for (D)component, an acyl oxime type (ketooxime is included) photoinitiator is preferable. Since an acyl oxime type|system|group photoinitiator has high sensitivity, the photosensitivity of curable resin composition can fully be improved, and the developability (resolution) of a cured resin film can fully be improved.

The O-acyl oxime type|system|group photoinitiator represented by General formula (9) or General formula (10) is contained in the example of an acyl oxime type|system|group photoinitiator.

In formula (9), R ₅ and R ₆ each independently represent an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R ₇ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or halogen, and the alkylene moiety is an unsaturated bond, an ether bond, or a thioether bond. , may contain an ester bond. In addition, the alkyl group in any one of linear, branched, or cyclic|annular form may be sufficient as an alkyl group.

(In formula (10), R ₈ and R ₉ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or 1 to 6 carbon atoms. is a phenyl group which may be substituted with two alkyl groups, R ₁₀ is each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and a part of the —CH ₂ — group in the alkyl or alkenyl group is an —O— group. may be substituted. In addition, some of the hydrogen atoms in these R ₈ to R ₁₀ groups may be substituted with halogen atoms)

In the present specification, the molar extinction coefficient of the photopolymerization initiator is measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Ellip Hi-Tech Science Co., Ltd.), the absorbance of an acetonitrile solution having a concentration of 0.001% by weight in a quartz cell with an optical path length of 1 cm. It can be measured and calculated as a value.

1-5. (E) sensitizer

(E) A sensitizer enables control of the hardening reaction by (D) a photoinitiator more precisely.

(E) Examples of the component include triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydro benzophenones such as hydroxybenzophenone and 4,4'-diethylaminobenzophenone; Acetophenone such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyldimethyl ketal argument; Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, 2-dimethylaminoethyl benzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid (n-butoxy ) Ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropyl thioxanthone, 4-benzoyl-4'-methyl -benzophenones such as diphenylsulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone , thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone systems, such as thioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone, Aminobenzophenone systems, such as 4,4'- bisdiethylamino benzophenone, 10 -Butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc. are included. In addition, these sensitizers may be used individually by 1 type, and may use 2 or more types together.

1-6. (F) solvent

(F) The solvent (hereinafter also referred to simply as "component (F)") dissolves or disperses each component contained in each composition and enhances the applicability of each composition.

(F) Examples of the component include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone and di alcohols such as acetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, and esters such as butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Each composition can be made into a uniform solution phase by melt|dissolving and mixing using these.

1-7. other ingredients

Each composition can mix|blend a thermal polymerization inhibitor, antioxidant, a chain transfer agent, a plasticizer, a filler, a leveling agent, an antifoamer, surfactant, a coupling agent, etc. as needed.

Hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert- butylcatechol, phenothiazine, a hindered phenol type compound etc. are contained in the example of a thermal polymerization inhibitor and antioxidant.

Examples of chain transfer agents include 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[ (3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3) -mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, thiol compounds, such as laurylthiopropionic acid, etc. are contained.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include glass fibers, silica, mica, alumina, and the like.

The compound of a silicone type, a fluorine type, and an acryl type is contained in the example of an antifoaming agent and a leveling agent.

Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like.

Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane etc. are included.

2. First Initiation

2-1. composition

The first indication in this specification is,

(A) an unsaturated group-containing polymerizable compound;

(B) an ultraviolet absorber;

(F) a solvent;

including,

(B) Content of a ultraviolet absorber relates to the composition for sclerosing|hardenable adhesive bond layer formation which are 10 mass % or more and 80 mass % or less with respect to the total mass of solid content. The said composition for adhesive bond layer formation may also contain (C) the epoxy compound which has two or more epoxy groups, (D) a photoinitiator, (E) a sensitizer, etc. as needed.

According to the composition for forming an adhesive layer according to the first disclosure, peeling of the adherend by laser irradiation of 355 nm is easy, and the adhesiveness and solvent resistance of the adherend to the adhesive layer are good.

In addition, the composition for adhesive bond layer formation may contain only (A1) component, may contain only (A2) component, and may use (A1) component and (A2) component together.

2-1-1. Preferred compounds for first disclosure

[(A2) component]

In the case of using (A2), from the viewpoint of further improving the adhesiveness of the cured film to the adherend, the component (A2) is preferably an alkylene oxide-modified or lactone-modified compound. These modified substances improve the fluidity of the composition for forming an adhesive layer at the interface with the adherend, and fill the minute gap between the adherend and the composition for forming the adhesive layer to increase the contact area (adhesion area), It is thought that the adhesiveness of the cured film with respect to a complex is improved more. In particular, when the component (B) is a compound having a high molecular weight, the component (A2), which is the modified product, compensates for the decrease in fluidity of the composition for forming an adhesive layer due to the component (B), so that the adhesive improvement effect is remarkable.

The modified alkylene oxide is preferably a compound having an alkylene oxide group having 2 or more and 6 or less carbon atoms, more preferably a compound having an alkylene oxide group having 2 or more and 4 or less carbon atoms, and has 2 or more carbon atoms. It is more preferable that it is a compound which has 3 or less alkylene oxide groups.

The lactone-modified product is a compound having a ring-opened structure in which lactones having 2 to 6 carbon atoms are ring-opened (-C(=O)-(CH ₂ ) _k -O-, where k is a number less than the number of carbon atoms in the lactone by one) Preferably, it is a compound having a ring-opened structure in which lactones having 4 to 6 carbon atoms are ring-opened, and more preferably a compound having a structure in which lactones having 6 carbon atoms are ring-opened.

The structure in which the said alkylene oxide group and the lactone ring-opened may exist independently in a molecule|numerator, and although 2 or more and 6 or less said alkylene oxide group or lactone may be continuous, it exists independently, or two said alkyl It is preferable that a lenoxide group or a lactone is continuous.

The modified product can be, for example, a compound represented by the following general formula (11).

In Formula (11), V is independently group which has the structure which the alkylene oxide group or lactone ring-opened. a to e are independently an integer of 0 to 6, provided that at least one of a to e is an integer of 1 to 6. As for a-e, 1 or 2 is preferable. R ₁₁ to R ₁₅ are independently preferably a (meth)acryloyl group or a hydroxyl group, provided that at least two of R ₁₁ to R ₁₅ are (meth)acryloyl groups. It is preferable that all of R5 _{- R9} are (meth)acryloyl groups. T is a group selected from the group consisting of a substituted or unsubstituted 1-4 valent hydrocarbon group, -O- and -S-, preferably a substituted or unsubstituted divalent hydrocarbon group, -O- and -S-, - O- is more preferable. q is independently 0 or 1, with 0 being preferred. r is an integer of 1-4 similar to the valence of Z, and 2 is preferable.

Examples of the modified product represented by the general formula (11) include ethylene oxide-modified dipentaerythritol hexaacrylate, dipentaerythritol dicaprolactone hexaacrylate, diphenane erythritol tricaprolactone hexaacrylate, and dipentaerythritol hexaprolactone hexaacrylate. Acrylate, dipentaerythritol polycaprolactone hexaacrylate (all manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane propylene oxide modified triacrylate, and trimethylolpropane ethylene oxide modified triacrylate (all manufactured by Dong-A Synthetic Co., Ltd.) .

Examples of the modified product other than the compound represented by the general formula (9) include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified di and triacrylate, diglycerin Ethylene oxide-modified acrylates (all manufactured by Dong-A Synthesis Co., Ltd.) and alkylene oxide-modified hexa(meth)acrylates of phosphagen are included.

[(A) component (common to (A1) component / (A2) component)]

The component (A) may be a resin in which the cured product obtained by the polymerization reaction of the polymerizable unsaturated group absorbs an appropriate amount of electromagnetic waves (preferably electromagnetic waves having a wavelength in the ultraviolet region), thereby degrading or decomposing the resin. For example, the component (A) may be a compound in which the obtained cured product is a resin containing a polymerizable unsaturated group and a repeating structure containing a conjugated π-electron system such as a benzene ring, a condensed ring and a heterocyclic ring in the molecule. . In addition, the said benzene ring, the condensed ring, and the heterocyclic ring may be substituted. For example, component (A) may be a compound from which a resin having a repeating unit containing a fluorene structure is obtained as the cured product, benzophenone structure, diphenylsulfoxide structure, diphenylsulfone structure, diphenyl structure, The compound from which resin which has a diphenylamine structure, a benzotriazole structure, etc. in a side chain is obtained may be sufficient.

[(B) component]

1st indication WHEREIN: (B) component (ultraviolet absorber) absorbs a laser favorably in the cured film formed by hardening|curing the composition for adhesive bond layer formation, and it heat|fever-generates. And (A) component is changed in quality by this heat|fever, and a cured film is peeled.

The component (B) may be a compound having an absorption peak between a wavelength of 250 nm or more and 450 nm or less, preferably 300 nm or more and 450 nm, but an adhesive layer capable of peeling off an adherend by a longer wavelength laser (for example, 355 nm, etc.) From a viewpoint of making formation possible, it is preferable that the absorbance of the light with a wavelength of 355 nm of component (B) is 0.10 or more, It is more preferable that it is 0.12 or more, It is still more preferable that it is 0.15 or more. The absorbance can be measured using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Ellip Hi-Tech Science Co., Ltd.), the absorbance of an acetonitrile solution having a concentration of 0.001% by weight in a quartz cell with an optical path length of 1 cm. In addition, when it is difficult for (B) component to melt|dissolve in acetonitrile, you may measure the absorbance of the solution made to melt|dissolve in propylene glycol monomethyl ether acetate instead.

In addition, when an alkali-soluble resin having a repeating unit containing a fluorene structure is used as the component (A1), compatibility with the component (A1) is good, it is difficult to increase the haze value of the cured film, and the solvent resistance of the cured film is improved. Since it is difficult to reduce, the compound which has a benzotriazole structure and a benzophenone structure is preferable, and the compound which has a benzotriazole structure (hydroxyphenylbenzotriazole structure) is more preferable.

Moreover, from a viewpoint of suppressing the bleedout of (B) component from a cured film when hardening an adhesive agent, as for (B) component, it is preferable that a weight average molecular weight (Mw) is a polymeric ultraviolet absorber of 1000 or more. The polymeric ultraviolet absorber can be a homopolymer of a compound having the above structure (particularly preferably a benzotriazole structure) and a polymerizable unsaturated group, or a copolymer of the compound and another monomer.

In addition, according to the knowledge of the present inventors, the polymeric ultraviolet absorber increases the heat resistance of the cured film, but on the other hand, it tends to decrease the adhesiveness (fluidity) of the composition for forming an adhesive layer to an adherend and the solvent resistance of the cured film. . On the other hand, in this embodiment, in order to ensure the adhesiveness to a to-be-adhered body by hardening of (A) component, and also to ensure solvent resistance, the fall of the said adhesiveness and solvent resistance does not become a problem easily. The said adhesive and solvent-resistance collateral effect is exhibited remarkably, when (A) component is a crosslinkable compound and forms a crosslinked structure at the time of hardening. In addition, as described above, if the component (A2) is an alkylene oxide-modified or lactone-modified modified product, the decrease in fluidity of the composition for forming an adhesive layer caused by a polymeric ultraviolet absorber is compensated for by these modified materials, so to avoid The adhesiveness of the cured film to a complex is also improved remarkably.

From the viewpoint of more fully obtaining the effect of improving the heat resistance, the weight average molecular weight (Mw) of component (B), which is a polymeric ultraviolet absorber, is preferably 1000 or more and 100000 or less, more preferably 5000 or more and 90000 or less, and 10000 or more. It is more preferable that it is 80000 or less.

In addition, the said weight average molecular weight can be made into the value obtained by measuring by gel permeation chromatography (GPC) measurement and converting into polystyrene. For example, using HLC-8220GPC (manufactured by Tosoh Corporation) as a column, any one of guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) The above-mentioned GPC can be performed by using more than one. As the eluent, THF (tetrahydrofuran) may be used.

2-1-2. compounding amount

In the composition for forming an adhesive layer, the content of component (A) is preferably 10% by mass or more and 90% by mass or less with respect to the total mass of the solid content, more preferably 20% by mass or more and 80% by mass or less, and attaching importance to adhesive strength In this case, it is more preferable that they are 40 mass % or more and 80 mass % or less. When the content of the component (A) is 10% by mass or more, the adhesiveness of the cured film to the adherend increases, and the cured film absorbs the irradiated laser (for example, ultraviolet rays) and is easily altered or decomposed. It becomes easier to isolate|separate a complex. Moreover, if it is 90 mass % or less, since the hardness (crosslinking density) of the adhesive bond layer after hardening does not become high too much, when light is irradiated, it is easy to ablate, and a residue is hard to generate|occur|produce.

When the (A1) component and the (A2) component are used together, the content of the component (A2) in the composition for forming an adhesive layer is 5 parts by mass or more and 1000 parts by mass or less when the total mass of the component (A1) is 100 parts by mass. It is preferable, It is more preferable that they are 10 mass parts or more and 600 mass parts or less, It is still more preferable that they are 20 mass parts or more and 300 mass parts or less. (A2) Since there exists enough polymerizable unsaturated group which occupies for resin as the said content of a component is 5 mass parts or more, since sufficient crosslinked structure can be formed, chemical-resistance improves. Moreover, if it is 1000 mass parts or less, since the crosslinking density of the adhesive bond layer after hardening is sufficient, when light is irradiated, it is easy to ablate, and it is hard to produce a residue.

When photoprocessability and heat resistance are calculated|required, it is preferable that content of (A2) component is 20 mass parts or more and 100 mass parts or less, when the total mass of (A1) component is 100 mass parts.

When the tackiness at room temperature is required, using the component (A2) alone, or when the total mass of the component (A1) is 100 parts by mass, 100 parts by mass or more and 1000 parts by mass or less (A2) is used in combination with the component. desirable.

(B) Content of a component is 10 mass % or more and 80 mass % or less with respect to the total mass of solid content. The improvement effect of the peelability by (B) component absorbs an ultraviolet-ray becomes higher, so that there is more said content. On the other hand, the bleed-out of (B) component at the time of high temperature and the fall of the solvent resistance of a cured film are hard to become a problem, so that there is little said content. From the viewpoint of balancing these, the content of component (B) is preferably 20 mass % or more and 65 mass % or less with respect to the total mass of the solid content, and when it is desired to emphasize adhesive strength more, it is 20 mass % or more and 45 mass % or less It is preferable, and when it wants to attach importance to peelability more, it is preferable that they are 35 mass % or more and 65 mass % or less.

(C) It is preferable that they are 0 mass parts or more and 60 mass parts or less with respect to the total mass of solid content, and, as for content of a component, it is more preferable that they are 5 mass parts or more and 50 mass parts or less. (C) If content of a component is 5 mass parts or more, sufficient crosslinked structure can be formed and chemical-resistance can be improved more. Moreover, since the crosslinking density of the adhesive bond layer after hardening does not become too high that content of (C)component is 60 mass parts or less, when light is irradiated, it is easy to ablate, and a residue is hard to produce.

(D) When the total mass of the component (A) is 100 parts by mass, the content of the component (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.3 parts by mass or more and 20 parts by mass or less. (D) When the said content of a component is 0.1 mass part or more, photopolymerization can be accelerated|stimulated and the speed|rate of photopolymerization can be made fast. Moreover, when the said content of (D)component is 30 mass parts or less, excessive increase of a sensitivity is suppressed, and when irradiating light and ablation, it can make it difficult to produce a burning, a peeling residue, etc. In addition, the composition for forming an adhesive layer preferably contains the component (D) when the pattern is formed by photolithography, but when the pattern is not formed or when the pattern is formed by a method other than photolithography (D) ) does not need to contain any ingredients.

Moreover, in this indication, when patterning an adhesive bond layer, it is preferable that the molar extinction coefficient in 365 nm of (D)component is 10000 L/mol*cm or more. Since such a photoinitiator has high sensitivity, even if it is a curable resin composition containing the component (A2) whose acrylic equivalent is comparatively large, sufficient photosensitivity can be ensured and the developability (resolution) of curable resin composition can fully be improved. Examples of such a photopolymerization initiator include Omnirad1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company) and Adeka Arc Rouge NCI-831 (manufactured by ADEKA, Inc., "Adeka Arc Rouge" is a registered trademark of the company), etc. This is included.

(E) When the total mass of component (D) makes 100 mass parts, it is preferable that they are 0.5 mass part or more and 400 mass parts or less, and, as for content of (E) component, it is more preferable that they are 1 mass part or more and 300 mass parts or less. (E) When the said content of component is 0.5 mass part or more, the sensitivity of (D)component can be improved, and the speed|rate of photopolymerization can be made fast. Moreover, when the said content of (E) component is 400 mass parts or less, excessive increase of a sensitivity can be suppressed, and when irradiating light and ablation, it can make it hard to produce a crushing, peeling residue, etc.

Although content of (F) component changes with the target viscosity of curable composition, etc., it is preferable that they are 50 mass % or more and 90 mass % or less with respect to the total mass of curable composition.

2-2. Method for manufacturing a laminate

A method for producing a laminate according to another embodiment of the first disclosure includes the steps of (1) providing the above-described composition for forming an adhesive layer on at least one surface of a support and an adherend to form an adhesive layer; (2) and adhering the support and the adherend through the formed adhesive layer. Hereinafter, each process is demonstrated.

[Step of Forming Adhesive Layer]

The formation process of an adhesive bond layer is a process of forming the adhesive bond layer containing the composition for adhesive bond layer formation mentioned above on the surface of at least one of a support body and a to-be-adhered body.

(support)

The type of the support is not limited as long as an adhesive layer can be formed on the surface thereof.

In this embodiment, it is preferable that the said support body has laser transmittance. In particular, the support preferably transmits light (laser) with a wavelength of 10 nm or more and 450 nm or less, and more preferably transmits light (laser) of a wavelength of 100 nm or more and 450 nm or less, and a wavelength of 350 nm or more and 450 nm or less It is particularly preferable to transmit light (laser) of Examples of the support having the laser transmittance include a glass substrate, an acrylic substrate, a sapphire substrate, and a quartz glass substrate. However, for a glass substrate and an acrylic substrate, it is necessary to use the board|substrate of a composition with sufficient transmittance|permeability of the wavelength of the light to be used. It is preferable that it is a glass substrate from an inexpensive point among the said support bodies.

The support is preferably a support having a transmittance of light having a wavelength of 350 nm or more and 450 nm or less in the entire range of the wavelength of 70% or more. The support having the transmittance can sufficiently transmit a long-wavelength laser (eg, 355 nm, etc.) irradiated from the support side to reach the adhesive layer.

The said transmittance|permeability can be measured as a numerical value when the transmittance|permeability of air|atmosphere is made into a baseline using ultraviolet-visible-infrared spectrophotometer "UH4150" (made by Illip High-tech Science Co., Ltd.).

(Adhesive)

Examples of the adherend include a semiconductor wafer, a semiconductor chip, a light emitting element, an optical system glass wafer, a metal foil, a polishing pad, a resin coating film, a wiring layer, and the like.

(Adhesive layer)

An adhesive bond layer is formed by providing the composition for adhesive bond layer formation to the surface of at least one of the above-mentioned support body and above-mentioned to-be-adhered body. As for the composition for adhesive bond layer formation, the cured film after hardening sufficiently absorbs a long-wavelength laser (for example, 355 nm etc.). Therefore, even by irradiation of a long-wavelength laser, it is sufficiently ablated and the adherend can be easily peeled off (excellent in laser workability).

Examples of the method for applying the adhesive include a known solution immersion method, a spin coat method, an inkjet method, a spray method, and a method using a roller coater, a land coater, a slit coater, and a spinner machine.

In the above application method, an adhesive layer is formed by drying the solvent (prebaking) after applying the adhesive. In addition, prebaking is performed by heating with an oven, a hotplate, etc. The heating temperature and heating time in a prebaking are suitably selected according to the solvent to be used, For example, it is performed at the temperature of 60-110 degreeC for 1 to 10 minutes.

The thickness of the adhesive layer can be arbitrarily selected. In this embodiment, it is preferable that they are 0.1 micrometer or more and 50 micrometers or less, and, as for the thickness of an adhesive bond layer, it is more preferable that they are 0.5 micrometer or more and 30 micrometers or less. If the thickness of the adhesive layer is 0.1 μm or more, the adhesive layer may have sufficient holding force to adhere the adherend. Moreover, if it is 50 micrometers or less, an adhesive bond layer can fully be hardened by light or thermosetting.

In addition, in this process, after providing an adhesive agent to the surface of either one or both of the above-mentioned support body and the above-mentioned to-be-adhered body, you may have the exposure process and the image development process for patterning an adhesive bond layer. By patterning the adhesive layer, the adhesive layer can be formed only on the portion where the adherend is adhered, and the peeling failure or misalignment of the adherend in the step of separating the support and the adherend (described later) can be suppressed. .

Examples of the light used in the exposure process include visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like. The light is preferably ultraviolet (wavelength 250-400 nm). In addition, in the developing process, a developing solution suitable for alkali development is used. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. Although these developing solutions can be suitably selected according to the characteristic of a resin layer, you may add surfactant as needed. The developing temperature is preferably 20°C or more and 35°C or less, and a fine image can be precisely formed using a commercially available developing machine, ultrasonic cleaner, or the like. In addition, after alkali development, it washes with water normally. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid filling) developing method, etc. are applicable.

[Step of adhering support and adherend]

The step of bonding the support and the adherend is a step of bonding the above-mentioned support and the adherend through the adhesive layer.

An example of the method of adhering the support and the adherend includes a method of contacting an adherend (a surface in contact with the adhesive layer is provided with an adhesive) to the surface of an adhesive layer formed on the surface of the support and pressing while heating. Included. Moreover, as for the adhesion conditions of a support body and to-be-adhered body, it is preferable that the temperature at the time of pressurization is room temperature or more and 200 degrees C or less, and it is more preferable that they are 30 degrees C or more and 150 degrees C or less. It is preferable that they are 0.01 MPa or more and 20 MPa or less, and, as for the pressure at the time of adhesion|attachment, it is more preferable that they are 0.03 MPa or more and 15 MPa or less. Further, if necessary, the adhesive layer may be thermosetted at a temperature of 120°C or higher and 250°C or lower after completion of the pressure thermocompression bonding. By bonding the support and the adherend under the above conditions, the adherend is firmly fixed by the surface of the support through the adhesive layer.

In the above bonding step, the support and the adherend may be bonded by photocuring. As an example of a method of photocuring the adhesive layer, there is a method of irradiating light using a high-pressure mercury lamp. Moreover, it is preferable that the wavelength of the light to irradiate is 200 nm or more and 500 nm or less as adhesion conditions of a support body and to-be-adhered body. It is preferable that they are 25 mJ/cm ² or more and 3000 mJ/cm ² or less, and, as for the exposure amount of the light to irradiate, it is more preferable that they are 50 mJ/cm ² or more and 2000 mJ/cm ² or less.

In this way, a laminate having a support, an adherend, and an adhesive layer comprising a cured product of the above-described composition for forming an adhesive layer disposed between the support and the adherend is formed.

2-3. How to treat the laminate

A method for treating a laminate according to an embodiment of the present invention includes (1) preparing the above-mentioned laminate, and (2) irradiating light to the laminate to separate the support and the adherend. do. Hereinafter, each process is demonstrated.

[Process of preparing a laminate]

The process of preparing a laminate is a process of forming a laminate as described above or preparing a laminate that has already been formed.

[Step of separating the support and the adherend]

The step of separating the support and the adherend is a step of separating the support and the adherend by irradiating the adhesive layer with light.

The irradiated light is not particularly limited as long as the support and the adherend can be separated. In this embodiment, it is preferable that the said light is an ultraviolet-ray. The wavelength of the light is more preferably 10 nm or more and 450 nm or less, still more preferably 100 nm or more and 450 nm or less, and particularly preferably 350 nm or more and 450 nm or less. When the wavelength of the light is 10 nm or more, the polymer, which is a component of the adhesive layer, absorbs light, thereby degrading or decomposing, and the strength and adhesion are reduced, so that the support and the adherend can be easily separated. Moreover, since the adhesive bond layer of a process part absorbs light as the wavelength of the said light is 450 nm or less, it can suppress that the residue of a cured film generate|occur|produced. Moreover, since an inexpensive glass substrate and an acrylic substrate, especially a glass substrate can be used as the wavelength of the said ultraviolet-ray is 350 nm or more, running cost can be suppressed.

Examples of the light source include a low mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and a laser light source such as far ultraviolet rays. The light source is preferably a laser light source irradiating a laser.

Examples of the laser include a solid laser, a liquid laser, and a gas laser. Further, examples of the solid-state laser include a semiconductor excitation laser and the like. Examples of liquid lasers include dye lasers and the like. Examples of the gas laser include an excimer laser and the like. Among them, the laser is preferably a semiconductor excitation laser.

Examples of the semiconductor excitation laser include Nd:YAG laser, Nd:YLF laser, Nd:glass laser, Nd:YVO ₄ laser, Yb:YAG laser, Yb:doped fiber laser, Er:YAG laser, Tm:YAG laser, etc. This is included. Examples of excimer lasers include KrF lasers, XeCl lasers, ArF lasers, F2 lasers, and the like. Among them, the laser is preferably an Nd:YAG laser.

In addition, although the output and the amount of integrated light irradiated to the adhesive layer differ depending on the type of light source, etc., when the irradiated light is a laser, the output may be 0.1 mW or more and 200 W or less. In addition, it is preferable that the amount of integrated light is 1 mJ/cm ² or more and 50 J/cm ² or less. If the amount of integrated light is 0.1 mJ/cm ² or more, burning, peeling residue, etc. generated during ablation are unlikely to occur. If it is 50J/cm ² or less, the speed of ablation can be appropriately controlled and appropriate processing can be performed.

When irradiating light (laser) to an adhesive bond layer, it is preferable to irradiate a laser to the whole surface of an adhesive bond layer from the side of a support body. The method of irradiating a laser is not specifically limited, It can carry out by a well-known method.

This embodiment may also include the process of processing the prepared laminated body before the process of isolate|separating a support body and a to-be-adhered body.

Methods of processing the laminate include dicing, thinning of an adherend such as backside grinding, photofabrication, lamination of semiconductor chips, mounting of various elements, resin encapsulation, and the like.

Moreover, this embodiment may also include the process of moving the said laminated body processed from one apparatus to another apparatus. As a method of moving the said laminated body, the moving method by a robot arm, etc. are contained.

In this way, the laminate of the present embodiment is processed.

3. Second Initiation

(2nd task)

As described in patent document 3 and patent document 4, as a resin composition for microlens formation, both the resin composition in which positive pattern formation is possible, and the resin composition in which negative pattern formation is possible are known.

However, according to the knowledge of the present inventors, the conventional resin composition described in patent document 3, patent document 4, etc. had the problem that a residue was easy to generate|occur|produce at the time of image development. In addition, when the distance between lenses is narrow, microlenses may be connected by this residue. On the other hand, it is also calculated|required that the formed microlens pattern has favorable adhesiveness to the board|substrate of the resin composition for microlens formation.

The invention according to the second disclosure in the present specification was made in view of such a point, and it is possible to form a microlens pattern with less limitation in the resin that can be used, less likely to cause residue during development, and good adhesion to the substrate. To provide a composition for forming microlenses that can be formed, a method for producing microlenses using the composition, a cured film formed by curing the composition, a solid-state imaging device having the microlens, and an imaging device having the solid-state imaging device do.

3-1. composition

The second disclosure in the present specification for solving the second problem is,

(A1) an unsaturated group-containing polymerizable compound which is an alkali-soluble resin;

(A2) an unsaturated group-containing polymerizable compound having no alkali-soluble group;

(B) an ultraviolet absorber;

(C) an epoxy compound having two or more epoxy groups;

(D) a photoinitiator;

(F) comprising a solvent;

(B) Content of a ultraviolet absorber relates to the composition for microlens formation which are 3 mass % or more and 20 mass % or less with respect to the total mass of solid content.

According to the composition for forming microlenses according to the second disclosure, it is possible to form a microlens pattern with less limitation in the resin that can be used, less leaving a residue during development, and good adhesion to the substrate.

3-1-1. Preferred compounds for second disclosure

[(B) component]

In the production of a conventional microlens, in the case of forming a negative pattern, after reaching the interface of the substrate, the composition is formed at the interface with the substrate even in the portion not irradiated with radiation by the radiation extending along the interface. There were cases where it hardened. It is thought that this expanded resin which hardened|cured resin expands along a base material interface by this will become a residue. On the other hand, in the second disclosure, component (B) (ultraviolet absorber) absorbs the irradiated radiation and suppresses the expansion of the surplus radiation along the substrate interface. Therefore, when the composition for microlens formation contains (B) component, it is thought that generation|occurrence|production of the residue peculiar to the time of negative pattern formation can be suppressed. Moreover, it is thought that the coupling|connection of microlenses which generate|occur|produces when the distance between lenses is narrow by suppression of a residue can also be suppressed.

(B) It is preferable that a component is a benzotriazole compound, a benzophenone compound, or a triazine compound. These ultraviolet absorbers can efficiently absorb the energy of radiation (for example, ultraviolet rays), suppress the expansion of excess radiation along the substrate interface, and reduce the occurrence of residues at the ends of the pattern after development.

Moreover, it is preferable that it is a compound which has a photosensitive functional group, and, as for (B) component, it is more preferable that they are a benzotriazole compound, a benzophenone compound, and a triazine compound which have a photosensitive functional group. It is preferable that the said photosensitive functional group is an ethylenically unsaturated group from a viewpoint of improving the reactivity of (A1) component and (A2) component. Examples of the ethylenically unsaturated group include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a styrenyl group, and the like. Among these, the highly reactive acryloyl group and methacryloyl group of (A1) component and (A2) component are preferable. By using the ultraviolet absorber which has an ethylenically unsaturated group, the photosensitive reactive group of a ultraviolet absorber, and (A1) component or (A2) component react, and a ultraviolet absorber can be contained in resin. Thereby, from the viewpoint of reducing heat damage to the substrate, even when the composition is cured at a low temperature such as 140° C., the seepage of the ultraviolet absorber to the solvent can be suppressed, and the chemical resistance of the cured product can be improved. Moreover, coloring by precipitation of a ultraviolet absorber, sublimation at the time of baking, etc. can also be suppressed.

Examples of the benzotriazole compound, benzophenone compound, and triazine compound having an ethylenically unsaturated group include 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole do.

In addition, RUVA-93 (made by Daechong Chemical Co., Ltd.) etc. are contained in the example of the commercial item of the said ultraviolet absorber.

3-1-2. compounding amount

(A1) It is preferable that they are 10 mass % or more and 90 mass % or less with respect to the total mass of solid content, and, as for content of a component, it is more preferable that they are 30 mass % or more and 80 mass % or less. (A1) When the content of the component is 10% by mass or more, the development adhesion is excellent even in a fine pattern, and peeling of the pattern can be suppressed, and when it is 90% by mass or less, good photocurability is exhibited, The contrast of the exposed portion and the unexposed portion is excellent, and sufficient photolithographic properties can be obtained.

(A2) As for content of component, 1 mass part or more and 200 mass parts or less are preferable with respect to 100 mass parts of (A1) component, 4 mass parts or more and 100 mass parts or less are more preferable, 10 mass parts or more and 70 mass parts or less are more preferably. (A2) When content of a component is 1 mass part or more with respect to 100 mass parts of (A1) component, the exposure sensitivity by (A2) component and the improvement effect of developability are fully exhibited. Further, when the content of the component (A2) is 200 parts by mass or less with respect to 100 parts by mass of the component (A1), the acidic functional group concentration is sufficiently high, and a desired pattern is obtained from the viewpoint of obtaining good solubility in the alkali developer in the exposed part. can form.

(B) Content of component is 3 mass % or more and 20 mass % or less with respect to the total mass of solid content, It is preferable that they are 4 mass % or more and 20 mass % or less, It is more preferable that they are 6 mass parts or more and 18 mass parts or less. When the content of the component (B) is 3% by mass or more, the amount of radiation extending along the substrate interface can be reduced, and it is possible to reduce the occurrence of residues at the end portions of the pattern after development. When content of (B) component shall be 20 mass % or less, since reaction of the part irradiated with radiation can fully advance, the composition for microlens formation can fully be hardened.

(C) It is preferable that they are 1 mass part or more and 30 mass parts or less with respect to the total mass of solid content, and, as for content of a component, it is more preferable that they are 3 mass parts or more and 20 mass parts or less. Chemical resistance can be further improved by making content of the epoxy compound of (C) component 1 mass part or more, and adhesiveness with a board|substrate can fully be ensured by content of the epoxy compound of (C) component being 30 mass parts or less. have.

(D) It is preferable that they are 0.1 mass part or more and 30 mass parts or less with respect to 100 mass parts of total amounts of (A1) component and (A2) component, and, as for content of component, it is more preferable that they are 0.3 mass part or more and 20 mass parts or less. (D) When content of component is 0.1 weight part or more, especially in the upper surface (irradiation side of a radiation) of a composition, photopolymerization can be advanced more fully. Moreover, when content of (D)component is 30 weight part or less, hardening reaction becomes difficult to advance to a coating-film deep part, and it becomes easy to form a lens shape by a heat flow.

(E) 0.5 mass part or more and 200 mass parts or less are preferable with respect to a total of 100 mass parts of (D)component, and, as for content of a component, 1 mass part or more and 100 mass parts or less are more preferable. (E) When the content of the component is 0.5 parts by mass or more, the photoinitiator can be sufficiently activated by light irradiation, and by setting it to 200 parts by mass or less, the curing reaction by the photoinitiator can be more precisely controlled. .

(F) It is preferable that content of component is 40 mass % or more and 80 mass % or less with respect to the total mass of the composition for microlens formation. (F) When content of component is 40 mass % or more, it can be set as the viscosity which makes it easy to apply|coat the composition for microlens formation on a board|substrate, and when it is 80 mass % or less, a coating film excellent in film thickness uniformity can be obtained.

2-2. Method for preparing a composition for microlens

The manufacturing methods (1)-(3) of the composition for microlenses in 2nd indication are demonstrated below.

[Method for manufacturing microlens (1)]

A method for producing a composition for microlens according to an embodiment of the present invention includes (i) a coating film layer forming step of applying the above-described composition for forming microlenses and drying the composition to form a coating film of the composition for forming microlenses, ( ii) an exposure step of irradiating a part of the coating film with radiation through a photomask, (iii) a development step of developing the coating film irradiated with radiation and removing the unexposed portion, (iv) thermally flowing the exposed portion after development, and It includes a heat flow process of heat-hardening the exposed part while processing it into a microlens shape. Hereinafter, each process is demonstrated.

[coating film layer forming process]

The coating film layer formation process is a process of apply|coating the above-mentioned composition for microlens formation on a base material, drying it, and forming a coating film layer.

A well-known thing can be used for the said base material. Examples of the substrate include a glass substrate, a silicon wafer, a plastic substrate, and a substrate on which a colored resist, an overcoat, an antireflection film, and various metal thin films are formed on their surfaces. Examples of the plastic substrate include a resin substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide. The substrate may be provided with a light-receiving element such as a photodiode, a light-emitting element such as an organic light-emitting element, or a dye-containing element such as a color filter.

A method of applying the composition for forming a microlens may use a known coating method. Examples of the coating method include a known solution immersion method, a spray method, a roller coater, a land coater, a slit coater, a spinner, and the like. By these methods, the composition for forming microlenses can be applied to a desired thickness.

As a drying method of the composition for forming microlenses applied by the above-described method, a known drying method may be used. The drying method may be performed by heating in an oven, a hot air blower, a hot plate, an infrared heater, or the like, vacuum drying, or a combination thereof. The heating temperature and heating time of the resin film can be appropriately selected according to the solvent to be used. It is preferable to perform the said heating temperature and heating time at 80-120 degreeC for 1 to 10 minutes, for example.

[Exposure process]

The exposure step is a step of irradiating a part of the above-mentioned coating layer with radiation through a photomask, and photocuring a part of the coating layer (composition for forming a microlens).

As the photomask, a known one may be used. Examples of the photomask include a multi-tone mask such as a halftone mask and a gray tone mask. In the gray tone mask, a light-shielding portion and a diffraction grating are formed on a light-transmitting substrate. In the diffraction grating, the interval between the light transmission regions such as slits, dots, and mesh is equal to or less than the resolution limit of the light used for exposure, and the transmittance of the light is controlled by the above configuration. In the halftone mask, a light-shielding portion and a semi-transmissive portion are formed on a light-transmitting substrate. The transmittance of the light used for exposure is controlled by the semi-transmissive part.

Examples of the radiation to be irradiated include visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like. Among the above-mentioned radiation, it is preferable that it is an ultraviolet-ray. In addition, a well-known exposure apparatus (an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a deep ultraviolet lamp, etc.) can be used for the apparatus which irradiates a radiation. Moreover, it is preferable that the wavelength of the radiation to irradiate is 250 nm or more and 400 nm or less. It is preferable that they are 25 mJ/cm ² or more and 3000 mJ/cm ² or less, and, as for the exposure amount of a radiation, it is more preferable that they are 50 mJ/cm ² or more and 2000 mJ/cm ² or less.

[Development process]

A developing process is a process of alkali-developing the coating film irradiated with radiation, and removing the coating film of an unexposed part.

Examples of the developing method of the coating film include a shower developing method, a spray developing method, a dip (immersion) developing method, and a puddle (liquid filling) developing method. In addition, the said developing method can be performed using a commercially available developing machine, an ultrasonic cleaning machine, etc.

Further, examples of a developer suitable for development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo and an aqueous solution of an alkali (basic compound) such as [5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane. Although developing conditions differ with the composition for microlens formation, it is 20-30 degreeC, and it is preferable to carry out for 10 to 120 second.

[thermal flow process]

The thermal flow process is a process of heat-hardening the exposed part (coating film) after image development while processing the exposed part into a microlens shape by performing a melt flow and thermal flow.

The method of heat-flowing the exposed part after development can be performed by a well-known method (heating by an oven, a hot-air blower, a hotplate, an infrared heater, etc., vacuum drying, or a combination thereof). The temperature of heat flow will not be restrict|limited in particular, if it is the temperature which a coating film melt-flows. The temperature of the heat flow is preferably performed at a temperature of 140 to 250°C for 10 to 120 minutes, and more preferably at a temperature of 180 to 230°C for 30 to 90 minutes.

By using the composition for forming microlenses of the present invention, even when pattern formation of microlenses by a negative photolithography method as in the production method (1) is performed, the expansion of radiation along the substrate interface is suppressed, and the pattern after development is suppressed. Since the residue on the edge part is reduced, it is suppressed that microlenses are connected, and the microlens pattern of a more favorable shape can be formed.

[Method for manufacturing microlens (2)]

Although the composition for forming microlenses of the present invention can sufficiently exhibit the effect of suppressing residues in the above manufacturing method (1), it is also suitable for formation of microlenses by the following manufacturing method (2) or manufacturing method (3). Can be used.

The method for producing a composition for microlenses according to an embodiment of the present invention comprises (i) applying the composition for forming microlenses, irradiating radiation, and curing the composition to form a resin layer of the composition for forming microlenses. A layer forming step, (ii) a step of forming an etching resist layer on the surface of the resin layer, (iii) an exposure step of irradiating a part of the etching resist layer with radiation through a photomask; A developing step of developing the etching resist layer; (v) a thermal flow step of thermally flowing the exposed portion after development and processing the exposed portion into a microlens shape; (vi) dry etching of the resin layer as a mask layer for the exposed portion after thermal flow and transferring the shape of the mask layer to the resin layer.

[resin layer forming process]

The resin layer forming process is a process of forming a resin layer of the composition for forming microlenses by applying the composition for forming microlenses on the surface of a substrate, irradiating radiation, and drying the composition. In the above step, before applying the composition for forming microlenses, the unevenness of the surface of the substrate is embedded and planarized by applying a transparent resin to the spin coat. Then, after the composition for forming microlenses is applied to the surface of the flattened substrate, radiation (eg, ultraviolet rays) is irradiated and thermosetted to form a resin layer. In addition, the method of applying the composition for microlens formation, the method of irradiating the applied composition for microlens formation, and the method of irradiating can be performed by the method similar to the method used by the above-mentioned manufacturing method (1). The said thermosetting may be performed by the usual method of thermosetting (post-baking) the composition containing an alkali-soluble resin and an epoxy resin.

[Step of Forming Etching Resist Layer]

The step of forming an etching resist layer is a step of forming an etching resist layer on the surface of the resin layer.

The component of the etching resist is not particularly limited as long as the shape can be transferred to the resin layer as a mask layer in the transfer step to be described later. The etching resist may be a positive resist or a negative resist. In addition, a well-known method can be used for the method of forming an etching resist layer on the surface of a resin layer.

[Exposure process]

The exposure process is a process of irradiating a part of the etching resist layer with radiation through a photomask, and photocuring a part of the etching resist layer. In addition, the method of exposing an etching resist layer is the same method as the method used by the above-mentioned manufacturing method (1), and conditions, such as temperature, can be changed suitably according to the kind of etching resist, and can be performed.

[Development process]

The developing process is a process of alkali-developing the etching resist layer irradiated with radiation. When the etching resist is positive, the exposed portion is removed, and when the etching resist is negative, the exposed portion is removed. What is necessary is just to select the method of alkali development suitably from well-known methods according to the kind of etching resist.

[thermal flow process]

A thermal flow process is a process of heat-flowing the exposed part of the etching resist layer after image development, making it melt-flow, and processing the exposed part of an etching resist layer into microlens shape. In addition, the heat flow process can be performed by changing suitably conditions, such as temperature, according to the kind of etching resist by the method similar to the method used by the manufacturing method (1) mentioned above.

[Transfer process]

A transfer process is a process of dry-etching the said resin layer as a mask layer in the exposed part of the etching resist layer after heat flow, and transferring the shape of the said mask layer to the said resin layer.

A well-known method can be used for the said dry etching. Examples of the dry etching method include plasma etching, ion etching, reactive ion etching, sputter etching, and the like. In addition, a well-known apparatus can be used for dry etching. Examples of the gas that can be used for dry etching include fluorine-based gases such as CHF ₃ , CF ₄ , C ₂ F ₆ , C ₃ F ₈ , and SF ₆ , chlorine-based gases such as Cl ₂ and BCl ₃ , O ₂ , O ₃ , and the like. of oxygen-based gases, H ₂ , NH ₃ , CO, CO ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ , C ₂ H ₆ , C ₃ H ₄ , C ₃ H ₆ , C ₃ H ₈ , HF, reducing gases such as HI, HBr, HCl, NO, NH ₃ , and BCl ₃ , and inert gases such as He, N ₂ and Ar are included. These gases can be mixed and used.

[Method for manufacturing microlenses (3)]

In the method for producing a composition for microlens according to an embodiment of the present invention, (i) coating the composition for forming microlenses on a lens material layer and drying the coating film to form a coating film of the composition for forming microlenses Step, (ii) an exposure step of irradiating a part of the coating film with radiation through a photomask, (iii) a development step of developing the coating film irradiated with radiation to remove an unexposed portion, (iv) the coating film after the development A mask layer forming step of thermally flowing, heat curing the coating film while processing it into a microlens shape, and forming a mask layer having a microlens pattern, (v) dry etching the lens material layer and the mask layer, and applying the coating and a transfer step of transferring the shape of the film layer to the lens material layer.

[coating film forming process]

The coating film forming process is a process of applying the composition for forming a microlens on a lens material layer, drying the composition, and forming a coating film of the composition for forming a microlens. At this time, the surface of the lens material layer is planarized by the same method as described in the method (2) for manufacturing the microlens. In addition, the method of apply|coating the composition for microlens formation and the method of drying the apply|coated composition for microlens formation can be performed by the method similar to the method used by the above-mentioned manufacturing method (1).

The lens material layer may be a layer made of a known lens material.

[Exposure process and development process]

The (ii) exposure step and (iii) development step can be performed in the same manner as described in the method for manufacturing a microlens (1).

[Mask layer forming process]

The mask layer forming step is a step of thermally flowing and melt-flowing the coating film after development, heat curing the coating film while processing it into a microlens shape, and forming a mask layer having a microlens pattern. The heat flow of the said coating film can be performed by the method similar to the method used by the manufacturing method (1) mentioned above.

[Transfer process]

The transfer step can be performed by the same dry etching method as the method used in the above-mentioned manufacturing method (2).

By using the composition for forming microlenses of the present invention, even in a method in which the composition for forming microlenses is used as a resist material as in the manufacturing method (3), the expansion of radiation along the interface between the lens layer and the etching resist layer is suppressed, Generation of residues at the ends of the resist pattern can be suppressed. Therefore, when the hardened|cured material of the composition for microlens formation of this invention is used as a mask, a lens layer can be etched accurately, and the microlens pattern of a more favorable shape can be formed.

2-3. solid-state imaging device

The solid-state imaging element in 2nd indication has the above-mentioned microlens. The solid-state imaging device of the present invention can achieve high pixel resolution and high sensitivity for having the above-mentioned microlenses.

2-4. imaging device

The imaging device in the second disclosure includes the above-described solid-state imaging device. The imaging device of the present invention can obtain a high-quality image for having the above-described solid-state imaging device.

2-5. Example of the second form

As a 2nd aspect based on the said technical thought, the following content can be illustrated.

[1] A composition for forming a microlens for forming a microlens pattern, comprising:

(A1) an unsaturated group-containing polymerizable compound which is an alkali-soluble resin;

(A2) an unsaturated group-containing polymerizable compound having no alkali-soluble group;

(B) an ultraviolet absorber;

(C) an epoxy compound having two or more epoxy groups;

(D) a photoinitiator;

(F) solvent

including,

The content of the (B) ultraviolet absorber is 3% by mass or more and 20% by mass or less with respect to the total mass of the solid content, the composition for forming a microlens.

[2] The composition for forming microlenses according to [1], wherein the (A1) alkali-soluble resin, the unsaturated group-containing polymerizable compound, is a resin represented by the following general formula (1).

(In the formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atom to which it is bonded is a linear or branched alkyl group having 1 to 10 carbon atoms, and 6 to 10 carbon atoms. It may be substituted with a group selected from the group consisting of an aryl group or an arylalkyl group, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, R ₁ each independently represents 2 carbon atoms to 4 alkylene groups, and l is each independently a number from 0 to 3. G is each independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one is a substituent represented by the following general formula (4). n is the average value This is a number from 1 to 20)

(in formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, and R ₄ is a divalent alkylene group having 2 to 20 carbon atoms. It is a saturated or unsaturated hydrocarbon group, and p is a number from 0 to 10)

(in formula (4), W is a divalent or trivalent carboxylic acid residue, and m is the number of 1 or 2)

[3] The composition for forming microlenses according to [1] or [2], wherein the (B) ultraviolet absorber is selected from the group consisting of a benzotriazole compound, a benzophenone compound, and a triazine compound.

[4] The composition for forming microlenses according to any one of [1] to [3], wherein the ultraviolet absorber (B) has an ethylenically unsaturated group.

[5] The (A1) alkali-soluble resin, the unsaturated group-containing polymerizable compound has a weight average molecular weight of 1000 or more and 40,000 or less, and an acid value of 50 mgKOH/g or more and 200 mgKOH/g or less, in any one of [1] to [4] The composition for forming a microlens as described.

[6] The composition for forming a microlens according to any one of [1] to [5], comprising a sensitizer as the component (E).

[7] A coating film layer forming step of applying the composition for forming a microlens according to any one of [1] to [6] and drying it to form a coating film of the composition for forming a microlens;

an exposure process of irradiating a part of the coating film with radiation through a photomask;

A developing step of developing the coating film irradiated with the radiation to remove the unexposed portion;

and a thermal flow step of thermally flowing the exposed portion after the development and heating and curing the exposed portion while processing the exposed portion into a microlens shape.

[8] A resin layer forming step of applying the composition for forming a microlens according to any one of [1] to [6], irradiating radiation and curing it to form a resin layer of the composition for forming a microlens;

forming an etching resist layer on the surface of the resin layer;

an exposure process of irradiating a part of the etching resist layer with radiation through a photomask;

a developing process of developing the etching resist layer irradiated with the radiation;

a thermal flow step of thermally flowing the exposed portion after the development and processing the exposed portion into a microlens shape;

and a transfer step of dry etching the resin layer as a mask layer in the exposed portion after the heat flow, and transferring the shape of the mask layer to the resin layer.

[9] A coating film forming step of applying the composition for forming microlenses according to any one of [1] to [6] on the lens material layer and drying the coating film to form a coating film of the composition for forming microlenses;

an exposure process of irradiating a part of the coating film with radiation through a photomask;

A developing step of developing the coating film irradiated with the radiation to remove the unexposed portion;

A mask layer forming step of thermally flowing the developed coating film, heat curing the coating film while processing it into a microlens shape, and forming a mask layer having a microlens pattern;

a transfer step of dry etching the lens material layer and the mask layer, and transferring the shape of the mask layer to the lens material layer;

A method of manufacturing a microlens comprising a.

[10] A cured film formed by curing the composition for forming a microlens according to any one of [1] to [6].

[11] A microlens comprising the cured film according to [10].

[12] The solid-state imaging device having the microlens according to [11].

[13] An imaging device including the solid-state imaging device according to [12].

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is concretely described based on an Example and a comparative example, this invention is not limited to these.

First, although demonstrated from the synthesis example of the unsaturated group containing alkali-soluble resin which is (A1) component, evaluation of resin in these synthesis examples was performed as follows, unless otherwise indicated.

In addition, about various measuring instruments, when the same model is used, the apparatus maker name is abbreviate|omitted from the 2nd place. In addition, in an Example, all the glass substrates used for preparation of the board|substrate with a cured film for a measurement give and use the same process. In addition, with respect to content of each component, when the first decimal place is 0, the description after a decimal point may be abbreviate|omitted.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated with a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and then heated at 160 ° C. for 2 hours [W ₂ (g)] saved from the formula.

Solid content concentration (wt%)=100×(W ₂ -W ₀ )/(W ₁ -W ₀ )

[acid]

The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution was obtained using a potentiometric titrator "COM-1600" (manufactured by Pyeongsang Industrial Co., Ltd.).

[Molecular Weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pcs.) + TSKgelSuper H-3000 (1 pcs.) + TSKgelSuper H-4000 (1 pcs.) pcs.) + TSKgelSuper H-5000 (1 pc.) (manufactured by Tosoh Corporation), temperature: 40°C, speed: 0.6 ml/min), and a weight average as a conversion value of standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) The molecular weight (Mw) was calculated|required.

The abbreviations described in the synthesis example are as follows.

BPFE: bisphenol fluorene type epoxy resin (in general formula (5), Ar is a benzene ring, l is 0 epoxy resin, epoxy equivalent 256 g/eq)

BNFE: bisnaphthol fluorene type epoxy resin (Epoxy resin in which Ar represented by the general formula (1) is a naphthalene ring and l is 0, epoxy equivalent 281 g/eq)

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP: triphenylphosphine

AA: acrylic acid

PGMEA: Propylene glycol monomethyl ether acetate

DCPMA: dicyclofentanyl methacrylate

GMA: glycidyl methacrylate

St: styrene

AIBN: Azobisisobutyronitrile

TDMAMP: trisdimethylaminomethylphenol

HQ : Hydroquinone

SA: succinic anhydride

TEA: triethylamine

[Synthesis Example 1]

In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were added, and at 100 to 105 ° C. The reaction product was obtained by stirring for 12 hours. Then, PGMEA (25.00 g) was thrown in, and it adjusted so that solid content might be 50 mass %.

Then, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain unsaturated group-containing curable resin (A1)-1. Solid content concentration of the obtained resin solution was 57.0 mass %, acid value (solid content conversion) was 96 mgKOH/g, and Mw by GPC analysis was 3600.

[Synthesis Example 2]

In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were added, and at 100 to 105 ° C. The reaction product was obtained by stirring for 12 hours. Then, PGMEA (25.00 g) was thrown in, and it adjusted so that solid content might be 50 mass %.

Next, BPDA (10.06 g, 0.03 mol) and THPA (11.89 g, 0.08 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing curable resin (A1)-2. Solid content concentration of the obtained resin solution was 57.0 mass %, acid value (solid content conversion) was 98 mgKOH/g, and Mw by GPC analysis was 2300.

[Synthesis Example 3]

In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were added, and at 100 to 105 ° C. The reaction product was obtained by stirring for 12 hours. Then, PGMEA (25.00 g) was thrown in, and it adjusted so that solid content might be 50 mass %.

Then, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing curable resin (A1)-3. Solid content concentration of the obtained resin solution was 56.3 mass %, acid value (solid content conversion) was 97 mgKOH/g, and Mw by GPC analysis was 4700.

[Synthesis Example 4]

In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (50.00 g, 0.09 mol), AA (12.82 g, 0.20 mol), TPP (0.23 g) and PGMEA (40.00 g) were added, and at 100 to 105 ° C. The reaction product was obtained by stirring for 12 hours. Then, PGMEA (25.00 g) was added to the said reaction product, and it adjusted so that solid content might become 50 mass %.

Next, BPDA (13.09 g, 0.04 mol) and THPA (6.77 g, 0.04 mol) were added to the obtained reaction product, stirred at 115 to 120° C. for 6 hours, and an unsaturated group-containing alkali-soluble resin (A1)-4 resin solution got The solid content concentration of the resin solution was 56.1 mass %, the acid value (solid content conversion) was 91 mgKOH/g, and Mw by GPC analysis was 3500.

[Synthesis Example 5]

PGMEA (300 g) was put in the 1 L 4-necked flask with a reflux condenser, and after nitrogen-substituting the inside of a flask system, it heated up at 120 degreeC. A mixture in which AIBN (10 g) was dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) in a flask was added dropwise from a dropping funnel over 2 hours, Furthermore, it stirred at 120 degreeC for 2 hours, and obtained the copolymer solution.

Then, after replacing the inside of the flask system with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution, and at 120° C. for 6 hours. It stirred to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the number of moles added to AA) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution, and reacted at 120°C for 4 hours to obtain an unsaturated group-containing curable resin (A1)-5 . Solid content concentration of resin solution was 46.0 mass %, acid value (solid content conversion) was 76 mgKOH/g, and Mw by GPC analysis was 5300.

1. Examples and comparative examples related to the first disclosure

The composition for adhesive bond layer formation was prepared by the compounding quantity (unit is mass %) of Tables 1-3. The compounding components used in Tables 1-3 are as follows.

(Polymerizable compound containing unsaturated group)

(A1)-1: resin solution obtained in Synthesis Example 1 (solid content concentration 57.0 mass%)

(A1)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 57.0 mass%)

(A1)-3: the resin solution obtained in Synthesis Example 3 (solid content concentration 56.3% by mass)

(A1)-5: resin solution obtained in Synthesis Example 5 (solid content concentration 46.0 mass%)

(A2)-1: A mixture of dipentaerythritol pentaacrylate and hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., “KAYARAD” is a registered trademark of the company)

(A2)-2: ethylene oxide 6 mol adduct of trimethylolpropane triacrylate (Aronix M-360, manufactured by Dong-A Synthesis Co., Ltd.)

(A2)-3: ethylene oxide 12 mol adduct of dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.)

(A2)-4: ε-caprolactone 6 mol adduct of dipentaerythritol hexaacrylate (KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.)

(Ultraviolet absorber)

(B)-1: RUVA-93(2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole, manufactured by Daechong Chemical Co., Ltd., molecular weight: 323.35, wavelength 355 nm absorbance of light: 0.25)

(B)-2: Tinuvin 477 (hydroxyphenyltriazine-based ultraviolet absorber, manufactured by BASF, solid content concentration of 80.0% by mass, molecular weight: 1100, light absorbance of 355 nm wavelength: 0.28)

(B)-3: UVA-5080(3-2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl=methacrylate and methyl methacrylate copolymer, Shinshinchon Manufactured by Chemical Industry Co., Ltd., solid content concentration of 41.0% by mass, molecular weight: 40,000 to 60,000, light absorbance of 355 nm wavelength: 0.16)

(B)-4: UVA-935LH (benzophenone-based polymer copolymer, manufactured by BASF, solid content concentration 30.0% by mass, light absorbance of 355 nm wavelength: 0.04)

(B) '-5: carbon black concentration 25.0 mass %, polymer dispersant concentration 4.0 mass %, PGMEA dispersion liquid (solid content 38.0 mass %) of dispersion resin (alkali-soluble resin (A1)-1 (solid content 9.0 mass %) of the synthesis example)

In addition, the absorbance is a value measured in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Ellip High-Tech Science Co., Ltd.), the absorbance of an acetonitrile solution having a concentration of 0.001% by weight. In addition, when (B) component was difficult to melt|dissolve in acetonitrile, the absorbance of the solution made to melt|dissolve in propylene glycol monomethyl ether acetate (PGMEA) was measured instead.

(solvent)

(F): propylene glycol monomethyl ether acetate (PGMEA)

[evaluation]

The following evaluation was performed using the cured film formed by hardening|curing the said composition for adhesive bond layer formation.

[Production of a substrate with a cured film for evaluation of transmittance and laser workability]

The composition for forming an adhesive layer shown in Tables 1 to 3 was subjected to a 125 mm x 125 mm synthetic quartz glass substrate (hereinafter referred to as "quartz glass substrate"), which was previously irradiated with ultraviolet rays with a wavelength of 254 nm and an illuminance of 1000 mJ/cm ² with a low-pressure mercury lamp to clean the surface. '), it was applied using a spin coater so that the film thickness after heat curing treatment became 1.0 µm, and prebaked at 90°C for 3 minutes using a hot plate to prepare a dry film. Then, main hardening (post-baking) was carried out at 250 degreeC for 30 minute(s) using a hot air dryer, and the board|substrate with a cured film (coating film) was obtained. In addition, the transmittance of light having a wavelength of 350 nm or more and 450 nm or less of the synthetic quartz glass substrate is 90% or more in the entire range of the wavelength.

In addition, the said transmittance|permeability is the value measured using the ultraviolet-visible-infrared spectrophotometer "UH4150" (made by Ellip High-tech Science Co., Ltd.), and taking the transmittance|permeability of a single quartz glass as a baseline.

[Transmittance evaluation]

The transmittance|permeability in wavelength 355nm and 400nm of the board|substrate with the said cured film after main hardening was measured using ultraviolet-visible-infrared spectrophotometer "UH4150" (made by Ellip High-tech Science Co., Ltd.).

[Laser workability (peelability) evaluation]

(Assessment Methods)

About the cured film after main hardening, the laser (laser wavelength: 355 nm) was irradiated from the quartz glass substrate side using flash lamp excitation Nd:YAG Q-SW laser oscillator "Callisto" (made by V Technology). The cured film was processed (coating film removal) by 100-600 mJ/cm< ² > laser energy, and the processed cured film was observed with the optical microscope. In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

◎: There is no coating film residue in the laser irradiation part at 400 mJ/cm ² or less

○: There is no coating film residue in the laser irradiation part at more than 400 mJ/cm ² and less than 500 mJ/cm ²

△: There is no coating film residue in the laser irradiation part at more than 500 mJ/cm ² and less than 600 mJ/cm ²

×: There is a coating film residue in the laser irradiation part at more than 600 mJ/cm ²

[Creation of a substrate with a cured film for evaluation of adhesive strength]

The composition for forming an adhesive layer shown in Tables 1 to 3 was applied on a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment became 5.0 µm, and then 3 at 90°C using a hot plate. Minute prebaking was performed to produce a dry film. Next, the glass substrate "#1737" cut to 2 mm x 2 mm was placed on the dry film, and it was heated for 1 minute on a 110 degreeC hotplate, and was temporarily bonded. Then, main hardening (post-baking) was carried out at 230 degreeC for 30 minute(s) using a hot air dryer, and the board|substrate with a cured film was obtained.

[Evaluation of adhesive strength (shear strength)]

(Assessment Methods)

About the 2 mm x 2 mm glass substrate "#1737" adhere|attached on the cured film, the test of adhesive strength was done with the die shear tester (made by Arctech Corporation). In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

(double-circle): adhesive strength is 10 MPa or more

(circle): Adhesive strength is 8 MPa or more and less than 10 MPa.

(triangle|delta): adhesive strength is 5 MPa or more and less than 8 MPa

x: adhesive strength is less than 5 MPa

[Preparation of a cured film for evaluation of heat resistance, compatibility evaluation, chemical resistance, and washability]

The composition for forming an adhesive layer shown in Tables 1 to 3 was applied on a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment became 5.0 µm, and then 3 at 90°C using a hot plate. Minute prebaking was performed to produce a dry film. Then, main hardening (post-baking) was carried out at 230 degreeC for 30 minute(s) using a hot air dryer, and the board|substrate with a cured film was obtained. In addition, at the time of heat resistance evaluation, the obtained cured film was scraped off, and it used for the measurement of TG-DTA.

[Heat resistance evaluation]

(Assessment Methods)

The powder of the obtained cured film was heated using a TG-DTA device "TG/DTA6200" (manufactured by Seiko Instruments Co., Ltd.) at a temperature increase rate of 5°C/min from 30°C to 400°C in air, and the weight of the sample was reduced by 5% temperature was measured. In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

○: 5% weight loss temperature is 280°C or higher

△: 5% weight loss temperature is 250°C or higher and lower than 280°C

×: 5% weight loss temperature is less than 250°C

[Compatibility evaluation]

(Assessment Methods)

The haze value was measured for the cured film (coating film) of the board|substrate with the obtained cured film using the turbidimeter "NDH5000" (made by Nippon Denshoku Industries Co., Ltd.). In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

(circle): The haze value of the board|substrate with a cured resin film is 10 or less

(triangle|delta): The haze value of the board|substrate with a cured resin film is more than 10 and 50 or less

x: The haze value of the board|substrate with a cured resin film is more than 50

[Evaluation of solvent resistance]

(Assessment Methods)

After immersing the cured film (coating film) of the board|substrate with the obtained cured film for 10 minutes in N-methylpyrrolidone, it wash|cleaned and dried. Then, the film thickness of the cured film (coating film) after a test was measured using the stylus-type level|step difference shape measuring apparatus "P-17" (made by KLA Tencol Co., Ltd.). In addition, more than (triangle|delta) was made into pass.

The residual film rate in chemical-resistance evaluation made the film thickness before a test L1, and made the film thickness after a test L2, and computed it from the following formula.

Remaining film rate (%)=L2/L1×100

(Evaluation standard)

○: Remaining film ratio is 90% or more

(triangle|delta): Remaining film ratio is 80 % or more and less than 90 %.

x: the remaining film rate is less than 80%

[Evaluation of cleanliness]

(Assessment Methods)

The cured film (coating film) of the board|substrate with the obtained cured film was immersed in cleaning liquid "NK poleve 480" (made by Nippon Kayaku Co., Ltd.) for 10 minutes at room temperature, and the cured film (coating film) was washed. Then, the glass substrate after a test was wash|cleaned and dried, and the presence or absence of the residue on a glass substrate was confirmed with the optical microscope. In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

(circle): A residue is not recognized on a glass substrate

(triangle|delta): A residue is confirmed in a part on a glass substrate

x: A residue is confirmed by the whole surface on a glass substrate

The evaluation results are shown in Tables 4 to 6.

As shown in Tables 4-6, it was confirmed that the laminated body which used the above-mentioned composition for adhesive bond layer formation for an adhesive bond layer was excellent in the processability (peelability) by the laser of wavelength 355nm. This is considered to be because the light of the said wavelength was efficiently absorbed by the adhesive bond layer by the addition of (B) component, and the adhesive bond layer changed quality and decomposed|disassembled.

Further, it was confirmed that a cured film excellent in adhesive strength and chemical resistance can be obtained while ensuring good laser workability (peelability) by setting the addition amount of component (B) to 10% by mass or more and 80% by mass or less with respect to the total mass of the solid content. It is thought that this is because the elution to a solvent is suppressed while thermosetting and improving the intensity|strength of a cured film by superposing|polymerizing the unsaturated group of (A1) component and (A2) component.

(A) By using the unsaturated group-containing curable resin represented by the general formula (1) as the component, heat resistance can be improved while maintaining laser releasability, and the process margin in the processing step of the laminate can be sufficiently increased can be obtained This is considered because it is excellent in thermal stability because unsaturated group containing curable resin represented by General formula (1) has many aromatic rings.

It was confirmed that it was excellent in the processability (peelability) by the laser of wavelength 355nm by using the ultraviolet absorber whose absorbance of the light of wavelength 355nm is 0.10 or more as (B) component. This is considered to be because (B) component absorbs light more efficiently, and it is because the quality change and decomposition|disassembly of an adhesive bond layer were accelerated|stimulated.

As shown in Examples 1 and 3 to 18, it was confirmed that, as component (B), the composition for forming an adhesive layer containing an ultraviolet absorber having a weight average molecular weight (Mw) of 1000 or more was excellent in heat resistance and solvent resistance. This is considered to be because the bleed-out of (B) component at the time of a heating and the elution to the solvent at the time of exposing to a solvent are suppressed.

As shown in Examples 14-16, it was confirmed that the composition for adhesive layer formation containing the alkylene oxide modified body of (meth)acrylate or caprolactone modified body as (A2) component was excellent in adhesive strength. This is considered to be because the fluidity|liquidity of the dry film|membrane at the time of heat bonding improves and follows a to-be-adhered body by including the compound with high fluidity|liquidity at the time of heating as (A2) component.

2. Examples and comparative examples related to the second disclosure

The compositions for forming microlenses of Examples 21-31 and Comparative Examples 21-23 were prepared by the compounding quantity (unit: mass %) of Tables 7 and 8. The compounding components used in Tables 7 and 8 are as follows.

(Polymerizable compound containing unsaturated group)

(A1)-1: resin solution obtained in Synthesis Example 1 (solid content concentration 57.0 mass%)

(A1)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 57.0 mass%)

(A1)-3: the resin solution obtained in Synthesis Example 3 (solid content concentration 56.3% by mass)

(A1)-4: resin solution obtained in Synthesis Example 4 (solid content concentration of 56.1% by mass)

(A1)-5: resin solution obtained in Synthesis Example 5 (solid content concentration 46.0 mass%)

(A2)-1: Dipentaerythritol penta/hexaacrylate mixture (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., “KAYARAD” is a registered trademark of the company)

(Ultraviolet absorber)

(B)-1: RUVA-93 (manufactured by Daechong Chemical Co., Ltd.)

(B)-6: Tinuvin 384-2 (manufactured by BASF Japan, solid content concentration of 95% by mass, “Tinuvin” is a registered trademark of the company)

(B)-7: Tinuvin 400 (solid content concentration 85% by mass)

(B)-8: ADEKA STAB 1413 (manufactured by ADEKA Co., Ltd., “ADEKA STAB” is a registered trademark of the company)

(epoxy compound)

(C): Biphenyl type epoxy resin (jER YX4000, manufactured by Samleung Chemical Co., Ltd., “jER” is a registered trademark of the company, epoxy equivalent 180-192 g/eq)

(Photoinitiator)

(D)-1: Omnirad907 (IGM Resins, manufactured by B.V., 「Omnirad」is a registered trademark of the company)

(D)-2: Irgacure OXE-01 (manufactured by BASF, “Irgacure” is a registered trademark of the company)

(sensitizer)

(E): michella ketone

(solvent)

(F): propylene glycol monomethyl ether acetate (PGMEA)

[evaluation]

The following evaluation was performed about the cured film formed by hardening|curing the composition for microlens formation of Examples 21-31 and Comparative Examples 21-23 which Tables 7 and 8 show.

(Preparation of a substrate with a cured film for measuring refractive index)

The compositions for forming microlenses shown in Tables 7 and 8 were coated on a 5-inch substrate (silicon wafer) using a spin coater so that the film thickness after heat curing became 1.0 μm, and using a hot plate at 100° C. for 5 minutes. It prebaked and produced the dry film. Then, the dried film was subjected to a photocuring reaction (exposure) by irradiating ultraviolet rays of 500mJ/cm ² with an ultra-high pressure mercury lamp (wavelength 365nm, illuminance 30mW/cm ² ), and then using a hot air dryer at 230 ° C. for 30 minutes, Main hardening (post-baking) was carried out, and the board|substrate with the cured film for refractive index measurement was obtained.

[Refractive index evaluation]

The refractive index in wavelength 633nm of the board|substrate with the said cured film after main hardening was measured using the ellipsometer (made by J.A. Woollam).

(Preparation of a substrate with a cured film for measuring transmittance)

The composition for forming microlenses shown in Tables 7 and 8 was spin-coated on a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Corporation) (hereinafter referred to as "glass substrate") so that the film thickness after heat curing was 1.0 µm. was applied, and prebaked at 100°C for 5 minutes using a hot plate to prepare a dry film. Next, the dried film was subjected to a photocuring reaction (exposure) by irradiating ultraviolet rays of 300mJ/cm ² with an ultra-high pressure mercury lamp (wavelength 365nm, illuminance 30mW/cm ² ), and then using a hot air dryer at 230° C. for 30 minutes. , the substrate with the cured film for the transmittance|permeability measurement was obtained by main hardening (post-baking).

[Transmittance evaluation]

The transmittance in wavelength 400nm of the board|substrate with the said cured film after main hardening was measured using the ultraviolet-visible-infrared spectrophotometer "UH4150 (made by Hitachi High-Tech Sciences).

(Preparation of a substrate with a cured film for pattern adhesion and pattern end residue evaluation)

The compositions for forming microlenses shown in Tables 7 and 8 were coated on a 125 mm x 125 mm glass substrate using a spin coater so that the film thickness after heat curing treatment was 2.0 μm, and using a hot plate at 100° C. for 5 minutes. It prebaked and produced the dry film. Next, the dried film was irradiated with ultraviolet rays of 300 mJ/cm ² with an ultra-high pressure mercury lamp (wavelength 365 nm, illuminance 30 mW/cm ² ), and photocuring reaction (exposure) was performed.

Subsequently, the exposed dry film (exposed film) was treated with 0.8% TMAH (tetramethylammonium hydroxide) developer at 23° C. at a shower pressure of 1 kgf/cm ² 10 from the development time (break time = BT) at which the pattern began to appear After the initial development treatment, spray water washing of 5 kgf/cm ² was performed, and the unexposed portion of the exposed film was removed to obtain a dot pattern having a diameter of 5 μm on the glass substrate. Finally, the board|substrate with the cured film for pattern adhesiveness and pattern edge part residue evaluation was obtained by main-curing (post-baking) the obtained dot pattern at 230 degreeC for 30 minute(s) using a hot air dryer.

[Pattern Adhesion Evaluation]

(Assessment Methods)

The presence or absence of peeling of the dot pattern was observed for the dot pattern (cured film) of a diameter of 5 micrometers on the said board|substrate using the optical microscope. In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

(circle): peeling is not recognized by the dot pattern

(triangle|delta): peeling is confirmed by a part of dot pattern

x: All of the dot patterns are peeling

[Evaluation of residues at the end of the pattern]

(Assessment Methods)

A dot pattern (cured film) having a diameter of 5 µm on the substrate was observed for the presence or absence of a residue at the end of the dot pattern using a scanning electron microscope (SEM). In addition, more than (triangle|delta) was made into pass.

(Evaluation standard)

(circle): Residue is not recognized in the pattern edge part

(triangle|delta): A residue is confirmed in a part of pattern edge part.

x: the residue of the pattern edge part is remarkable

(Production of a substrate with a cured film for evaluation of chemical resistance)

The compositions for forming microlenses shown in Tables 7 and 8 were coated on a glass substrate using a spin coater so that the film thickness after heat curing became 2.0 μm, and dried by prebaking at 100° C. for 5 minutes using a hot plate. curtain was made Then, the dried film was subjected to a photocuring reaction (exposure) by irradiating ultraviolet rays of 300mJ/cm ² with an ultra-high pressure mercury lamp (wavelength 365nm, illuminance 30mW/cm ² ), and then using a hot air dryer at 180° C. for 1 hour. Alternatively, main curing (post-baking) was performed at 230°C for 30 minutes to obtain a substrate with a cured film for evaluation of chemical resistance.

[Evaluation of solvent resistance]

(Assessment Methods)

The film thickness (L1) of the cured film after main curing (post-baking) and the film thickness (L2) of the cured film after immersion in acetone for 10 minutes, washing and drying, respectively, were measured using a stylus type step difference shape measuring device "P-17." ' (manufactured by KLA Tencol Co., Ltd.), and the remaining film rate (%) was calculated from the following formula. In addition, more than (triangle|delta) was made into pass.

Remaining film rate (%)=L2/L1×100

(Evaluation standard)

○: Remaining film ratio is 90% or more

(triangle|delta): The remaining film ratio is 80% or more and less than 90%

x: the remaining film rate is less than 80%

The evaluation results are shown in Tables 9 and 10.

As shown in Examples 21-31, it confirmed that the cured film which has a high refractive index and high transmittance|permeability could be formed by using the resin composition for microlens formation of this invention.

As shown in Examples 21-31, it was confirmed that generation|occurrence|production of the residue peculiar to the time of negative pattern formation can be suppressed by using the resin composition containing a ultraviolet absorber. This is because the ultraviolet absorber absorbs the irradiated radiation, suppresses the expansion of the surplus radiation along the substrate interface, and inhibits the curing of the composition at the interface with the substrate in the area not irradiated with radiation. I think.

Moreover, as shown in Examples 24-31, it confirmed that the chemical-resistance of hardened|cured material could be improved by using the ultraviolet absorber which has an ethylenically unsaturated group by suppressing the exudation to the solvent of a ultraviolet absorber. This is considered to be because the photosensitive reactive group of the ultraviolet absorber and the unsaturated group-containing alkali-soluble resin or photopolymerizable monomer react, and the ultraviolet absorber can be contained in the resin.

According to the first disclosure of the present invention, it is possible to provide a laminate having an adhesive that can be used in the manufacture of various products. In particular, it is possible to provide a laminate suitable for processing by temporarily fixing to a support such as a semiconductor wafer.

According to the second disclosure of the present invention, it is possible to provide a resin composition for forming a microlens that can be used for a solid-state imaging device requiring high pixelation and high sensitivity.

Claims (12)

A composition for adhering a support and an adherend, and forming an adhesive layer capable of separating the support and the adherend by irradiating light, the composition comprising:
(A) an unsaturated group-containing polymerizable compound;
(B) an ultraviolet absorber;
(F) comprising a solvent;
The content of the said (B) ultraviolet absorber is 10 mass % or more and 80 mass % or less with respect to the total mass of solid content, The composition for adhesive bond layer formation. The method of claim 1,
The (A) unsaturated group-containing polymerizable compound contains (A1) alkali-soluble resin,
The composition for forming an adhesive layer, wherein the component (A1) is a resin having a weight average molecular weight of 1000 or more and 40,000 or less. 3. The method of claim 1 or 2,
Said (A1) alkali-soluble resin is resin represented by following General formula (1), The composition for adhesive bond layer formation.

(In formula (1), Ar is independently an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and a part of the hydrogen atoms constituting Ar is an alkyl group having 1 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. may be substituted with a substituent selected from the group consisting of an aryl group or arylalkyl group _of It is independently an alkylene group having 2 or more and 4 or less carbon atoms. l is independently a number of 0 or more and 3 or less. G is independently a (meth)acryloyl group or the following general formula (2) or the following general formula (3) is a substituent represented by. Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is represented by the following general formula (4) It is a substituent, n is a number with an average value of 1 or more and 20 or less)

(In formulas (2) and (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or an alkylarylene group having 2 or more and 10 or less carbon atoms, and R ₄ is a C 2 or more or 20 or less alkylene group. It is a saturated or unsaturated hydrocarbon group, and p is a number from 0 to 10)

(in formula (4), W is a divalent or trivalent carboxylic acid residue, and m is the number of 1 or 2) 4. The method according to any one of claims 1 to 3,
The (A) unsaturated group-containing polymerizable compound includes (A2) an unsaturated group-containing polymerizable compound having no alkali-soluble group, the composition for forming an adhesive layer. 5. The method of claim 4,
The (A2) unsaturated group-containing polymerizable compound having no alkali-soluble group comprises a compound having an alkylene oxide-modified or lactone-modified (meth)acryloyl group, the composition for forming an adhesive layer. 6. The method according to any one of claims 1 to 5,
The (B) ultraviolet absorber has an absorbance of light having a wavelength of 355 nm of 0.10 or more, the composition for forming an adhesive layer. 7. The method according to any one of claims 1 to 6,
The (B) ultraviolet absorber is a compound having a weight average molecular weight (Mw) of 1000 or more, the composition for forming an adhesive layer. 8. The method according to any one of claims 1 to 7,
The (B) ultraviolet absorber is a compound having a benzotriazole structure, the composition for forming an adhesive layer. support and
adherend and
A laminate comprising an adhesive layer comprising a cured product of the composition for forming an adhesive layer according to any one of claims 1 to 8 disposed between the support and the adherend. 10. The method of claim 9,
The support is a support having a transmittance of light of a wavelength of 350 nm or more and 450 nm or less of 70% or more, a laminate. A step of forming an adhesive layer by applying the composition for forming an adhesive layer according to any one of claims 1 to 8 to the surface of at least one of the support and the adherend;
and adhering the support and the adherend through the formed adhesive layer. A step of preparing the laminate according to claim 9 or 10;
and a step of separating the support and the adherend by irradiating the adhesive layer with light.