WO2016152852A1 - Photosensitive resin composition, photosensitive element, mask material for sand blasting, and method for treating surface of object to be treated - Google Patents

Abstract

The present invention discloses a photosensitive resin composition which contains: component (A), a binder polymer; component (B), a photopolymerizable compound; component (C), a photopolymerization initiator; and component (D), a thermoplastic compound. Component (B) contains component (b1) that is at least two different urethane (meth)acrylates which include a urethane (meth)acrylate represented by general formula (I). (In the formula, R¹ denotes a divalent organic group, and R² denotes a group represented by general formula (II).) (In the formula, R³ denotes a hydrogen atom or a methyl group, X denotes an alkylene group, and n denotes an integer between 9 and 40.)

Description

Photosensitive resin composition, photosensitive element, mask material for sandblasting, and surface processing method for object to be processed

The present disclosure relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a mask material for sandblasting, and a surface processing method for an object to be processed.

Conventionally, as a method for selectively cutting a predetermined portion of a target object such as glass or ceramic, a photosensitive layer made of a photosensitive resin composition is provided as a mask material on the target object, and the photosensitive layer is patterned. A method is known in which, after forming a resist pattern (mask portion), a non-mask portion is selectively cut (that is, sandblasted) by spraying an abrasive, and then the resist pattern is peeled off.

A photosensitive resin composition used as a mask material for sandblast treatment is used as a photosensitive element in which a photosensitive layer made of a photosensitive resin composition is provided on a support, for example. As the photosensitive resin composition, a composition containing an alkali-soluble resin, urethane (meth) acrylate, and a photopolymerization initiator has been used. As the alkali-soluble resin, for example, carboxyl group-containing cellulose, carboxyl group-containing acrylic resin, and the like are used (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 3449572 Japanese Patent No. 3846958 Japanese Patent Laid-Open No. 6-161098 JP 2012-27357 A

For such a conventional photosensitive resin composition, when a photosensitive element is produced, it is difficult to peel the photosensitive layer from the support due to the stickiness of the photosensitive resin composition (adequate tackiness). There is no problem). Further, in order to increase the sandblast resistance (hereinafter sometimes simply referred to as “blast resistance”), it is considered necessary to reduce the elastic modulus of the sandblasting mask, which is a film after curing. When the blending amount of urethane (meth) acrylate is increased, the tackiness of the photosensitive layer increases at the stage before curing, and thus the photosensitive layer tends to be difficult to peel off from the support. As a result, it may be difficult to transfer the photosensitive layer to the object to be processed.

In order to make it easy to transfer the photosensitive layer to the object while maintaining blast resistance, for example, a water-soluble resin layer containing polyvinyl alcohol or partially saponified polyvinyl acetate, or polyvinyl glycol or partially saponified polyvinyl acetate with ethylene glycol It has been proposed to provide a water-soluble resin layer to which propylene glycol, polyethylene glycol or the like is added as a release layer, and to provide a release layer containing an alkali-soluble cellulose derivative (see, for example, Patent Documents 3 and 4).

However, the conventional photosensitive resin compositions described in Patent Documents 1 to 4 have insufficient adhesion to a base material such as a glass substrate, and it is difficult to form a pattern on such a base material. There's a problem. When an adhesion assistant or the like is used to improve the adhesion, alkali developability tends to be lowered and pattern formation tends to be difficult. On the other hand, the photosensitive resin composition is also required to easily peel the resist pattern from the object to be processed after the sandblast treatment, that is, to have excellent peelability.

Therefore, the present disclosure can easily peel the support from the photosensitive layer without providing a release layer, and forms a resist pattern having sufficiently good blast resistance and good release from the object to be processed. An object of the present invention is to provide a photosensitive resin composition. Moreover, the photosensitive element using the said photosensitive resin composition, the mask material for sandblasting, and the surface processing method of a to-be-processed object are also provided.

In one aspect of the present disclosure, (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: thermoplastic compound. A photosensitive resin composition containing two or more different urethane (meth) acrylates, wherein the component (B) contains (b1) component: urethane (meth) acrylate represented by the following general formula (I) Things are provided.

(In the formula, R ¹ represents a divalent group, and R ² represents a group represented by the following general formula (II).)

(In the formula, R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 9 to 40.)

In another aspect of the present disclosure, (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, (E) component: silane compound having a mercapto group And the component (B) contains two or more different urethane (meth) acrylates including the component (b1): the urethane (meth) acrylate represented by the general formula (I). A functional resin composition is provided.

In still another embodiment of the present disclosure, the component (A) includes: a binder polymer, component (B): a photopolymerizable compound, component (C): a photopolymerization initiator, and the component (B) (B1) component: two or more different urethane (meth) acrylates including the urethane (meth) acrylate represented by the general formula (I), and the content of the component (b1) is a photosensitive resin. A photosensitive resin composition is provided that is 3 to 20% by mass based on the total solid content of the composition.

According to the photosensitive resin composition, the support can be easily peeled from the photosensitive layer by having the above configuration, and a good pattern can be formed on a substrate such as a glass substrate, a silicon wafer, or a ceramic substrate. Can be formed. Moreover, according to the said photosensitive resin composition, the resist pattern which has favorable blast tolerance and favorable peelability from a to-be-processed object can be formed. Therefore, the photosensitive resin composition can be suitably used as a sandblast mask material.

The content of the component (B) may be 30 to 70% by mass based on the total solid content of the photosensitive resin composition. When it is 30% by mass or more, the peelability from the object to be processed is further improved, and when it is 70% by mass or less, the photosensitive resin composition is less likely to be highly fluidized and suppresses stickiness of the photosensitive resin composition. There is a tendency to be able to.

The photosensitive resin composition can further contain (D) component: a thermoplastic compound. The component (D) may contain an aromatic phosphate compound.

Further, the content of the component (D) may be 1 to 20% by mass based on the total solid content of the photosensitive resin composition. When it is 1% by mass or more, the elastic modulus of the film after curing can be made more appropriate, the blast resistance of the resist pattern is improved, and when it is 20% by mass or less, the photosensitive resin composition is high. It is difficult to fluidize and tends to suppress stickiness of the photosensitive resin composition.

The component (B) may also include urethane (meth) acrylate, which is a reaction product of the component (b2): a compound having a terminal isocyanate group and a (meth) acrylate compound having a hydroxyl group. The compound having a terminal isocyanate group is a reaction product of a diol compound and a diisocyanate compound. The weight average molecular weight of the component (b2) may be 2000 to 45000. When the weight average molecular weight is 2000 or more, the stickiness of the photosensitive resin composition tends to be further reduced. When the weight average molecular weight is 45000 or less, alkali developability is further improved, resist residue is hardly generated, and resolution is further improved. Tend to. Further, the content of the component (b2) may be 20 to 50% by mass based on the total solid content of the photosensitive resin composition.

The photosensitive resin composition may further contain a component (E): a silane compound having a mercapto group.

(E) By further containing a component, the adhesiveness of the photosensitive resin composition with base materials, such as a glass substrate, a silicon wafer, a ceramic substrate, improves, and a more favorable pattern can be formed. Moreover, since the elasticity modulus of hardened | cured material does not become high easily, the resist pattern formed from the photosensitive resin composition can have favorable blast resistance.

The content of the component (E) may be 0.01 to 10% by mass based on the total solid content of the photosensitive resin composition. When the content is 0.01% by mass or more, the adhesiveness of the photosensitive resin composition to the base material is further improved, and a better pattern tends to be formed. On the other hand, when the content is 10% by mass or less, there is a tendency that resist residues are not easily generated during alkali development.

The present disclosure also provides a photosensitive element comprising a support and a photosensitive layer containing the photosensitive resin composition on the support. According to such a photosensitive element, the stickiness of the photosensitive layer is small, and the support can be easily peeled from the photosensitive layer. Furthermore, according to the photosensitive element, a photosensitive layer having a uniform thickness can be obtained.

The present disclosure also includes forming a photosensitive layer containing the photosensitive resin composition on an object to be processed; irradiating the photosensitive layer with an actinic ray to form a photocured portion at a predetermined location; Removing the portion other than the photocured portion to form a resist pattern, and spraying an abrasive to cut the portion of the workpiece on which the resist pattern is not formed; Provide a processing method.

The present disclosure provides a sandblast mask material formed from the photosensitive resin composition. The photosensitive resin composition can form a good pattern on a substrate such as a glass substrate, and the formed resist pattern has good blast resistance. be able to. Moreover, the said photosensitive resin composition can be applied suitably for manufacture of the mask material for sandblasting.

According to the present disclosure, a photosensitive resin composition capable of easily peeling a support from a photosensitive layer and forming a resist pattern having sufficiently good blast resistance and good peelability from an object to be processed. Things can be provided. Furthermore, according to this indication, the photosensitive element using this photosensitive resin composition, the mask material for sandblasting, and the surface processing method of a to-be-processed object can be provided.

It is a schematic cross section which shows suitable one Embodiment of a photosensitive element. (A), (b) and (c) is a schematic cross section which shows suitable one Embodiment of a sandblasting process and a peeling process. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object. It is a model perspective view which shows suitable one Embodiment of the surface processing method of a to-be-processed object.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings depending on cases, but the present disclosure is not limited to the following embodiments. In the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified and clearly considered essential in principle. This also applies to numerical values and ranges, and should not be construed to unduly limit the present disclosure. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present specification, “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. In the present specification, “(meth) acrylate” means at least one of “acrylate” and “methacrylate” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic acid”. In this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended purpose of the process is achieved. included. In this specification, solid content refers to components in a composition other than a volatile substance such as water and a solvent, and does not necessarily mean a solid.

(Photosensitive resin composition)
The photosensitive resin composition of this embodiment includes a binder polymer (hereinafter also referred to as “component (A)”), a photopolymerizable compound (hereinafter also referred to as “component (B)”), and photopolymerization initiation. Agent (hereinafter also referred to as “component (C)”), and as component (B), urethane (meth) acrylate represented by the following general formula (1) (hereinafter referred to as “(b1) component”) 2 or more types of urethane (meth) acrylates containing the same. Moreover, the photosensitive resin composition of this embodiment may contain other components as needed.

Hereinafter, each component contained in the photosensitive resin composition according to the present embodiment will be described.

<(A) component: Binder polymer>
Although there is no restriction | limiting in particular as (A) component, From a viewpoint which alkali developability improves, what has a carboxyl group is preferable. Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, urethane resins, and cellulose derivatives having a carboxyl group. The component (A) preferably contains an acrylic resin having a carboxyl group or a cellulose derivative having a carboxyl group in that the alkali developability is further excellent. These can be used alone or in combination of two or more.

Examples of the cellulose derivative having a carboxyl group include cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate, and hydroxypropylmethylcellulose acetate succinate.

Examples of the acrylic resin having a carboxyl group include acrylic resins containing (meth) acrylic acid and alkyl (meth) acrylate as monomer units. In such an acrylic resin, a carboxyl group can be introduced by using (meth) acrylic acid as a monomer unit.

Examples of alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Examples include hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These can be used alone or in combination of two or more.

In addition to (meth) acrylic acid and alkyl (meth) acrylate, the acrylic resin having a carboxyl group used another monomer having an ethylenically unsaturated group (polymerizable monomer) as a monomer component. A copolymer may also be used. Examples of other polymerizable monomers include (meth) acrylic such as tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. Acid esters; maleic monomers such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; N-vinylcaprolactam; N-vinylpyrrolidone; styrene; vinyltoluene, p- Examples thereof include styrene derivatives such as methylstyrene, p-ethylstyrene, p-chlorostyrene, and α-methylstyrene. These can be used alone or in combination of two or more.

When the component (A) is an acrylic resin having a carboxyl group, from the viewpoint of improving alkali developability, the acid value of the component (A) is preferably 50 to 250 mgKOH / g, and preferably 70 to 230 mgKOH / g. More preferably, it is more preferably 100 to 200 mg KOH / g.

The acid value can be measured as follows. First, after precisely weighing 1 g of a solution containing a resin whose acid value is to be measured, 30 g of acetone is added to this resin solution to dissolve it. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. Then, the acid value is calculated by the following formula (α).

A = 10 × Vf × 56.1 / (Wp × I) (α)
In the formula (α), A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I Indicates the ratio (mass%) of the non-volatile content in the measured resin solution.

The weight average molecular weight (Mw) of the component (A) is preferably 20000 to 150,000, more preferably 30000 to 120,000 from the viewpoint of reducing stickiness of the photosensitive resin composition and improving alkali developability. It is preferably 40,000 to 100,000. In addition, a weight average molecular weight (Mw) can be measured by performing conversion by standard polystyrene using gel permeation chromatography (GPC).

The content of the component (A) in the photosensitive resin composition is preferably 20 to 60% by mass, and preferably 30 to 50% by mass, based on the total solid content of the photosensitive resin composition. More preferred. When the component (A) is 20% by mass or more, the stickiness of the photosensitive resin composition tends to be further reduced, and when it is 60% by mass or less, the resist pattern blast formed from the photosensitive resin composition There is a tendency for resistance to improve more.

<(B) component: photopolymerizable compound>
The component (B) is not particularly limited as long as it is a compound having photopolymerizability, and examples thereof include compounds having at least one ethylenically unsaturated bond. (B) component of the photosensitive resin composition which concerns on this embodiment is 2 or more types of different urethane containing at least 1 sort (s) of (b1) component: urethane (meth) acrylate represented by the following general formula (I). (Meth) acrylate is included.

In general formula (I), R ¹ represents a divalent organic group. The divalent organic group represented by R ¹ is not particularly limited as long as it contains a carbon atom and can link an isocyanurate ring and an amide group. The divalent organic group represented by R ¹ may be, for example, an alkylene group having 1 to 10 carbon atoms. The alkylene group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, heptylene group, octylene group, 2- Examples thereof include an ethyl-hexylene group, a nonylene group, and a decylene group. Three R ^{1 s} in the general formula (I) may be the same or different, but are preferably the same.

In the present embodiment, R ¹ is preferably an alkylene group having 2 to 7 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms, from the viewpoint of blast resistance and resolution.

In the general formula (I), R ² represents a polymerizable group represented by the following general formula (II). Three R ² in the general formula (I) may be the same or different, but are preferably the same.

In general formula (II), R ³ represents a hydrogen atom or a methyl group, and X represents an alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably an alkylene group having 2 to 7 carbon atoms from the viewpoint of releasability from the object to be processed and blast resistance of the resist pattern, and has 2 to 3 carbon atoms. An alkylene group is more preferable. Specific examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. The alkylene group may be linear or branched. Furthermore, ten or more Xs in the general formula (II) may be the same or different, but are preferably the same.

N represents an integer of 9 to 40. From the viewpoint of peelability from the object to be processed and blast resistance of the resist pattern, n is preferably an integer of 9 to 30. n may be an integer of 10 to 40, an integer of 10 to 25, or an integer of 15 to 25.

The component (b1) is, for example, a compound represented by any one of the following general formula (II-1), general formula (II-2), or general formula (II-3), and the following general formula (VI): It can be produced by reaction with the compound represented. R ³ and n in general formulas (II-1), (II-2) and (II-3) have the same meanings as R ³ and n in general formula (II), and R ³ and n in general formula (VI) ¹ has the same meaning as R ¹ in formula (I). The reaction conditions are not particularly limited as long as they are normal reaction conditions for generating a urethane bond, and the reaction may be performed using a catalyst or the like as appropriate. In addition, the terminal represented by general formula (VI) may be allophanatized.

In the photosensitive resin composition of the present embodiment, the content of the component (b1) is not particularly limited, but from the viewpoint of improving the peelability from the object to be processed and the blast resistance of the resist pattern. It is preferably 3 to 20% by mass, more preferably 5 to 10% by mass based on the total solid content of the product.

In the photosensitive resin composition of the present embodiment, the component (B) is represented by the above general formula (I), R ¹ is an alkylene group having 1 to 10 carbon atoms, and X is 2 to 3 carbon atoms. It is preferably an alkylene group containing 3 to 20% by mass of a compound having n of 9 to 40, represented by the above general formula (I), wherein X in R ¹ is an alkylene group having 2 to 3 carbon atoms. Thus, it is more preferable to contain 3 to 20% by mass of a compound having n of 15 to 25.

The photosensitive resin composition according to an embodiment of the present disclosure includes, for example, a diol compound and a diisocyanate compound as one of two or more different urethane (meth) acrylates, in addition to the component (b1). Use of urethane (meth) acrylate (hereinafter also referred to as “component (b2)”), which is a reaction product of a compound having a terminal isocyanate group, which is a reaction product, and a (meth) acrylate compound having a hydroxyl group. Can do. The component (b2) has a urethane bond and a (meth) acryloyl group. The component (b2) may be a polymer.

Examples of the diol compound include polyesters having a hydroxyl group at the terminal, polyethers, polycarbonates, and the like. Examples of polyesters are obtained by condensation reaction of alkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol with dicarboxylic acid such as maleic acid, fumaric acid, glutaric acid, and adipic acid. And polyesters obtained by ring-opening polymerization of lactones.

Examples of the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl-β. -Propiolactone, β, β-dimethyl-β-propiolactone and the like.

Examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride. Examples of the polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polypentamethylene glycol.

Examples of the diisocyanate compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2 , 5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nanomethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, isophorone diisocyanate, etc. Aliphatic or alicyclic diisocyanate compounds may be mentioned. These can be used alone or in combination of two or more.

Examples of the (meth) acrylate compound having a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and the like. These can be used alone or in combination of two or more.

Component (b2) is a reaction product of a terminal isocyanate group, which is a reaction product of a diol compound and a diisocyanate compound, and a reaction product of a (meth) acrylate compound having a hydroxyl group, and further an alkyl (meth) acrylate. It may be reacted. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

The weight average molecular weight of the component (b2) is preferably 2000 to 45000, more preferably 5000 to 43000, and still more preferably 10,000 to 40000.

The glass transition point after curing of the component (b2) is preferably 50 ° C. or lower.

The component (b2) preferably has two ethylenically unsaturated groups. The ethylenically unsaturated group can be derived from, for example, the (meth) acrylate compound having a hydroxyl group. When component (b2) has two ethylenically unsaturated groups, the elastic modulus of the film after curing is lowered, and the blast resistance of the resist pattern is further improved.

As the component (b2), for example, “KAYARAD UX-3204”, “KAYARAD UXF-4001-M35”, “KAYARAD UXF-4002” (manufactured by Nippon Kayaku Co., Ltd., trade name (“KAYARAD” is a registered trademark). )), “Purple light UV-3000B” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name (“purple light” is a registered trademark)), etc.

The content of the component (b2) is preferably 20 to 50% by mass, more preferably 30 to 40% by mass based on the total solid content of the photosensitive resin composition.

In addition, the component (B) in the present embodiment may include a photopolymerizable compound other than the above components (b1) and (b2) (hereinafter sometimes referred to as “other photopolymerizable compounds”). Good.
Examples of other photopolymerizable compounds include compounds obtained by reacting α, β-unsaturated carboxylic acids with polyhydric alcohols, and products obtained by adding α, β-unsaturated carboxylic acids to glycidyl group-containing compounds. Examples include compounds, alkyl esters of (meth) acrylic acid, phthalic acid esters of (meth) acrylic acid, (meth) acrylate compounds having a urethane bond, and bisphenol A (meth) acrylate compounds.

Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetrae Toxitri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate and the like.

Examples of compounds obtained by adding an α, β-unsaturated carboxylic acid to the glycidyl group-containing compound include bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, and bisphenol A. Examples include bisphenol A polyoxyethylene di (meth) acrylate such as decaoxyethylene di (meth) acrylate, (meth) acrylate adduct of trimethylolpropane triglycidyl ether, (meth) acrylate adduct of bisphenol A diglycidyl ether, etc. be able to.

Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like.

Examples of the phthalic acid ester of (meth) acrylic acid include γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethyl. -O-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, and the like.

Examples of the (meth) acrylate compound having a urethane bond include, for example, a (meth) acrylic monomer having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6- Addition reaction products with diisocyanate compounds such as hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. It is done. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. Examples of the EO-modified urethane di (meth) acrylate include the product name “UA-11” manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of the EO and PO-modified urethane di (meth) acrylate include “UA-13” manufactured by Shin-Nakamura Chemical Co., Ltd.

Examples of the bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynona) Toxi) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like.

Among the above-mentioned compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is, for example, “BPE-500” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or FA-321M (Hitachi). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane, for example, “BPE-1300NH” (Shin Nakamura Chemical Co., Ltd.) It is commercially available as a company-made product name. These may be used alone or in combination of two or more.

Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxide decapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like . These may be used alone or in combination of two or more.

Among these, from the viewpoint of releasability from the object to be processed and blast resistance of the resist pattern, it may contain at least one of a bisphenol A-based (meth) acrylate compound and a (meth) acrylate compound having a urethane bond. preferable. In addition, these are used individually or in combination of 2 or more types.

The content of component (B) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition. When the component (B) is 30% by mass or more, pattern formation becomes easier, and when it is 70% by mass or less, stickiness of the photosensitive resin composition tends to be further reduced.

<(C) component: photopolymerization initiator>
The component (C) is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators. For example, anthraquinone derivatives such as 2-methylanthraquinone, benzophenone derivatives such as 3,3-dimethyl-4-methoxy-benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,2′-bis (2-chlorophenyl)- Imidazole derivatives such as 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2-dimethoxy-2 -Acetophenone derivatives such as phenylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzoin alkyl ether derivatives such as benzoinpropyl ether, thioxanthone derivatives such as diethylthioxanthone, Michler's ketone, 9-phenylacridine Dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,4,6-trimethylbenzoyldiphenyl Examples thereof include phosphine oxide. These can be used alone or in combination of two or more.

From the viewpoint of further improving the photosensitivity, the content of the component (C) is preferably 0.1 to 10% by mass, based on the total solid content of the photosensitive resin composition, and is preferably 0.2 to 5% by mass. % Is more preferable.

<(D) component: thermoplastic compound>
The photosensitive resin composition which concerns on one Embodiment of this indication can further contain a thermoplastic compound. As the component (D), an aromatic phosphate ester compound may be included, and the aromatic phosphate ester compound may include a compound represented by the following general formula (III).

In the general formula (III), a plurality of R ⁴ may be the same or different. R ⁴ represents, for example, each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkyl mercapto group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a group containing a heterocyclic ring, etc. It's okay. m and n may each independently be an integer of 0 to 5.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine, astatine and the like. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl group. Octyl group, nonyl group, decyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like. The aryl group includes a halogen atom, an amino group, and a nitro group. , A cyano group, a mercapto group, an aryl group, an alkyl group having 1 to 20 carbon atoms, and the like. Examples of the alkyl mercapto group having 1 to 10 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group and the like. Examples of the carboxyalkyl group having 1 to 10 carbon atoms include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, and the like. Examples of the acyl group having 1 to 10 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, and pivaloyl group.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the group containing a heterocyclic ring include a furyl group, a thienyl group, a pyrrolyl group, a thiazolyl group, an indolyl group, a quinolyl group, and the like.

R ⁵ in the general formula (III) may be, for example, a phenylene group or a divalent group represented by the following general formula (IV).

In general formula (IV), R ⁶ may be, for example, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the general formula (III), R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms from the viewpoint of excellent manufacturability and availability, and m and n are each independently 2 Preferably there is. Further, among the compounds represented by the general formula (III), a compound represented by the following general formula (III) ′ is preferable from the viewpoint of further excellent manufacturability and availability.

(In Formula (III) ′, R ⁵ has the same meaning as R ⁵ in Formula (III), and R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

In the general formula (III) ′, when R ²² and R ²³ are an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, Examples include isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like, and methyl group is preferable from the viewpoint of availability. From the standpoint of flame retardancy, folding resistance, hydrolysis resistance, and electric corrosion resistance, it is more preferable that at least one of R ²² and R ²³ is an alkyl group having 1 to 4 carbon atoms.

As the compound represented by the general formula (III) ′, for example, R ⁵ is a group represented by the general formula (IV) (R ⁶ is a methyl group, respectively), R ²² is a methyl group, and R ²³ is hydrogen. A compound that is an atom, R ⁵ is a group represented by the general formula (IV) (R ⁶ is a methyl group, R ²² and R ²³ are each a methyl group, R ⁵ is a phenylene group, Examples thereof include compounds in which R ²² is a methyl group and R ²³ is a hydrogen atom, compounds in which R ⁵ is a phenylene group, and R ²² and R ²³ are methyl groups. As the component (D), “Adekastab FP-600” (aromatic phosphate ester, manufactured by ADEKA Corporation, trade name (“Adekastab” is a registered trademark)), CR-741 (aromatic phosphate ester, large It is commercially available as a product name of Hachi Chemical Industry Co., Ltd.

The content of component (D) is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content of the photosensitive resin composition. When the component (D) is 1% by mass or more, the blast resistance of the resist pattern is improved, and when it is 20% by mass or less, stickiness of the photosensitive resin composition tends to be suppressed.

<(E) component: silane compound having a mercapto group>
The photosensitive resin composition which concerns on one Embodiment of this indication can further contain the silane compound which has a mercapto group. (E) As a component, the compound represented by the following general formula (V) may be included.

In the general formula (V), R ⁷ represents an alkylene group having 1 to 6 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, and a propylene group. A represents an alkyl group. Specific examples thereof include a methyl group and an ethyl group.
B represents an alkoxy group, a chloro group, an alkoxyalkoxy group, an acetoxy group or an alkenyloxy group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alkoxyalkoxy group include a methoxyethoxy group. Examples of the alkenyloxy group include an isopropenoxy group. N represents an integer of 0 to 2, and is preferably 0 or 1 from the viewpoint of adhesion to the substrate.

As the component (E), a compound having a mercaptoalkoxy group and an alkoxy group (mercaptoalkylalkoxysilane) is preferable. Examples of such component (E) include mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and the like. Among these, mercaptopropyltrimethoxysilane which is easily hydrolyzed and capable of crosslinking at three points is preferable from the viewpoint of further improving the adhesion to the substrate.

The component (E) is commercially available, and examples thereof include “Z-6062”, “Z-6862”, “Z-6911” (trade name, manufactured by Toray Dow Corning Co., Ltd.) and the like. These can be used alone or in combination of two or more.

The content of the component (E) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is 5 to 3% by mass.

In addition, the photosensitive resin composition according to the present embodiment includes a dye such as malachite green, a photochromic agent such as leuco crystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, if necessary. Phthalocyanine-based organic pigments such as phthalocyanine blue, azo-based organic pigments, inorganic pigments such as titanium dioxide, silica, alumina, talc, calcium carbonate, barium sulfate and other fillers (excluding the above inorganic pigments), antifoaming agents, and stability Agents, adhesion-imparting agents, leveling agents, antioxidants, fragrances, imaging agents and the like. When these components are contained, it is preferably contained in an amount of about 0.01 to 20% by mass based on the total solid content of the photosensitive resin composition. Moreover, said component can be used individually by 1 type or in combination of 2 or more types.

Furthermore, the photosensitive resin composition according to the present embodiment may contain a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether as necessary. It can be dissolved in these mixed solvents and used as a solution having a solid content of about 30 to 70% by mass.

The photosensitive resin composition according to the present embodiment can form a good pattern on a substrate such as a glass substrate, a silicon wafer, or a ceramic substrate, and the resist pattern formed from the photosensitive resin composition is good. Therefore, it can be suitably used as a mask material for sand blasting. Moreover, the photosensitive resin composition which concerns on this embodiment can also be used with the form of the photosensitive element obtained by forming a photosensitive layer on a support body.

(Photosensitive element)
Next, the photosensitive element using the photosensitive resin composition which concerns on this embodiment mentioned above is demonstrated. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element according to this embodiment. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive layer 14 provided on the support 10. The photosensitive layer 14 is a layer containing the photosensitive resin composition according to the present embodiment described above. The photosensitive layer 14 may be a layer made of the photosensitive resin composition. In the photosensitive element 1 according to this embodiment, the surface F1 opposite to the surface in contact with the support 10 on the photosensitive layer 14 may be covered with a protective layer.

The photosensitive layer 14 can be formed by applying a solution of the above-described photosensitive resin composition onto the support 10 and drying it. The application can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like. The drying can be performed by heating and / or spraying with hot air at 70 to 150 ° C. for about 5 to 30 minutes.

The thickness of the photosensitive layer 14 varies depending on the use, but the thickness after drying is preferably 10 to 120 μm, more preferably 20 to 100 μm. When the thickness is within the above range, it tends to be industrially easy to apply. When the thickness is 10 μm or more, the blast resistance of the resist pattern tends to be improved, and when it is 120 μm or less, the resolution tends to be further improved.

Examples of the support 10 provided in the photosensitive element 1 include a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. Moreover, as a protective layer, a polymer film etc. can be used like a support body.

The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. When the thickness is 5 μm or more, the support tends to be hardly broken when the support is peeled before development, and when the thickness is 100 μm or less, the resolution tends to be further improved.

The photosensitive element 1 composed of two layers of the support 10 and the photosensitive layer 14 as described above or the photosensitive element composed of three layers of the support 10, the photosensitive layer 14 and the protective layer is stored as it is, for example. Alternatively, the protective layer may be interposed and wound around the core in a roll shape and stored.

(Surface processing method of workpiece)
The surface processing method of the to-be-processed object which concerns on this embodiment is the process (photosensitive layer formation process) of forming the photosensitive layer containing the above-mentioned photosensitive resin composition on a to-be-processed object, and an active ray to the said photosensitive layer Irradiation to form a photocured portion at a predetermined location (exposure step), removal of portions other than the photocured portion by development to form a resist pattern (development step), and spraying an abrasive to resist And a step (sand blasting step) of cutting a part to be processed where a pattern is not formed. Moreover, the surface processing method of the to-be-processed object which concerns on this embodiment may include the process (peeling process) of removing a resist pattern using a peeling liquid from the cut to-be-processed object after a sandblasting process process.

In the photosensitive layer forming step, the photosensitive layer can be formed by laminating the above-described photosensitive elements on the substrate in the order of the photosensitive layer and the support from the substrate side. In addition, before the said lamination | stacking, a protective layer can also be removed from the photosensitive element mentioned above as needed.

Examples of the laminating method include a method of laminating by pressing the photosensitive layer on the substrate while heating.

The heating temperature of the photosensitive layer at the time of the above lamination is preferably 70 to 130 ° C., and the pressing pressure is preferably about 0.1 to 1.0 MPa, but these conditions are not particularly limited. In addition, if the photosensitive layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material in advance, but in order to further improve the laminating property, the base material may be pre-heated. it can.

In the photosensitive layer forming step, the photosensitive layer may be formed by directly applying the above-described photosensitive resin composition onto a target object and drying it.

After forming the photosensitive layer in this way, a photocured portion is formed by irradiating a predetermined portion of the photosensitive layer with actinic rays in the exposure step. Examples of the method for forming the photocured portion include a method of irradiating actinic rays in an image form through a negative mask pattern called an artwork. At this time, when the support on the photosensitive layer is transparent, it can be irradiated with actinic rays as it is, but when it is opaque, it is irradiated with actinic rays after removing the support.

As the actinic ray light source, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp can be used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

Next, after the exposure, when a support is present on the photosensitive layer, after removing the support, in the development process, the photosensitive layer other than the photocured portion is removed by wet development, dry development, etc. A pattern is formed.

In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, or scrubbing, using a developer such as an alkaline aqueous solution. As the developer, a developer that is safe and stable and has good operability is used. For example, a dilute solution (1 to 5% by mass aqueous solution) of sodium carbonate at 20 to 50 ° C. is used.

In the sandblasting process, the obtained resist pattern is used as a mask material, and an abrasive is sprayed to cut a portion of the object to be processed on which the resist pattern is not formed. As a polishing agent (blasting material) used for sandblasting, various known ones are used. For example, fine particles of about 2 to 100 μm such as glass beads, SiC, SiO ₂ , Al ₂ O ₃ , and ZrO are used. As a to-be-processed object, base materials, such as a glass substrate, a silicon wafer, and a ceramic substrate, are mentioned, for example. The thickness of the object to be processed can be appropriately adjusted depending on the material of the object to be processed and the like, and can be, for example, 0.01 to 10 mm.

After cutting the object to be processed with an abrasive, a peeling process is performed to remove the resist pattern from the object to be processed using a peeling solution. Examples of the stripping solution used in the stripping step include alkaline aqueous solutions such as an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. In addition, a resist pattern can also be removed by providing the process of burning off a resist pattern at high temperature instead of a peeling process.

FIG. 2 is a schematic cross-sectional view showing a preferred embodiment of a sandblasting process and a peeling process. First, in the sand blasting process, the abrasive 18 is sprayed onto the object 16 through the resist pattern 19 to cut the portion of the object 16 where the resist pattern 19 is not formed (FIG. 2 (a)). The to-be-processed object 20 separated into pieces is obtained (FIG.2 (b)). Furthermore, the resist pattern 19 on the to-be-processed object 20 separated by the peeling process is peeled off (FIG. 2C).

As an example of the surface processing method of the object to be processed according to the present embodiment, an example in which the photosensitive resin composition described above is used as a mask material for sandblasting for separating a large glass into a cover glass is shown in FIGS. 6 will be described. 3 to 6 are schematic perspective views showing a process of dividing a large glass into a cover glass.

First, as shown in FIG. 3, a photosensitive layer 21 according to this embodiment is provided on a large glass (object to be processed) 22 (photosensitive layer forming step). Next, exposure and development are performed on the photosensitive layer provided on the large format glass 22 to form a resist pattern 24 having a desired shape as shown in FIG. 4 (exposure process and development process). Then, sand blasting is performed using the resist pattern 24 as a mask material, and the non-mask portion is cut to obtain a cover glass 26 in which the large glass 22 is separated into pieces as shown in FIG. 5 (sand blasting process). Finally, as shown in FIG. 6, the outer edge of each cover glass 26 is mechanically polished to smooth the cut surface. Such a processing method can be suitably used particularly for manufacturing a cover glass for a smartphone.

Hereinafter, the objects and advantages of the present disclosure will be described more specifically based on production examples and comparative examples. However, according to the specific materials and amounts thereof and other conditions and details listed in these examples, the present disclosure Should not be unduly restricted.

(Production Examples 1 to 9, Comparative Examples 1 to 5)
First, the photosensitive resin composition is prepared by blending each of the following components at a mass ratio shown in Tables 1 and 2 (however, when the component is blended as a solution, the mass ratio in terms of solid content). A solution containing was obtained.

(A) -1: Toluene / methyl cellosolve (mass ratio = 2/3) of acrylic resin obtained by copolymerization of methacrylic acid / ethyl acrylate / methyl methacrylate / styrene (mass ratio: 26/20/34/20) ) A solution (weight average molecular weight: 50000, solid content acid value: 170 mgKOH / g, solid content: 43% by mass) obtained by polymerization by a conventional method.
In addition, the weight average molecular weight in this specification can be obtained by measuring by a gel permeation chromatography method and converting with a calibration curve created using standard polystyrene. The measurement conditions in GPC are as follows.
Column: Gelpack GL-R440 + GL-R450 + GL-R400M (both manufactured by Hitachi Chemical Co., Ltd., trade name (“Gelpack” is a registered trademark))
Flow rate: 2.05 mL / min Concentration: 120 mg / 5 mL
Injection volume: 200 μL
Eluent: THF (tetrahydrofuran)
(B) -1: γ-Chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-MECH”)
(B) -2: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-321M”)
(B) -3: a compound represented by general formula (I) (component (b1)), wherein R ¹ is —C ₆ H ₁₂ — and R ² is n = 15. A compound in which X is an ethylene group and R ³ is a methyl group (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: “UA-HCY-19”)
(B) -4: a compound represented by the above general formula (I) (component (b1)), wherein R ¹ is —C ₆ H ₁₂ — and R ² is n = 10. A compound in which X is an ethylene group and R ³ is a methyl group (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: “UA-7100”)
(B) -5: Tris (methacryloyloxytetraethylene glycol isocyanate hexamethylene) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: “UA-21”)
(B) -6: a compound represented by the following general formula (VII), wherein R ⁵¹ and R ⁵² are groups represented by the following general formula (VIII), and R ⁵³ is the following general formula (IX) (Daicel Ornex Co., Ltd., trade name: “JTX0309”)

(B) -7: Urethane acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: “KAYARAD UX-3204”) weight average molecular weight: 13000, number of ethylenically unsaturated groups: 2, glass transition point after curing: − 14 ° C.) ((b2) component: polymer having urethane bond and (meth) acryloyl group)
(B) -8: Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: “Shigetsu UV-3000B”) weight average molecular weight: 18000, number of ethylenically unsaturated groups: 2, glass transition point after curing: −39 ° C.) (component (b2): polymer having urethane bond and (meth) acryloyl group)
In addition, the glass transition point after hardening can be measured with the following method. 100 g of a polymer having a urethane bond and a (meth) acryloyl group and 4 g of “Irgacure 184” (manufactured by BASF, trade name (“Irgacure” is a registered trademark)) as a photopolymerization initiator are mixed, and the thickness is 100 μm. A coating film was prepared so that the glass transition point was measured by a thermomechanical analysis (TMA) method after exposure at 500 mJ / cm ² .
(C) -1: 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (C) -2: 4,4′-bis (Diethylamino) benzophenone (D) -1: aromatic phosphate ester (manufactured by ADEKA Corporation, trade name: “ADK STAB FP-600”)
(E) -1: 3-Mercaptopropyltrimethoxysilane (made by Toray Dow Corning Co., Ltd., trade name: “Z-6062”)
(E) -2: 3-Ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBE-585”)
(X) -1: leuco crystal violet (X) -2: methyl ethyl ketone

Note) The symbol “-” in Table 1 and Table 2 indicates that the product does not contain the relevant component.

[Production of photosensitive element]
The obtained solution containing the photosensitive resin composition was separately made uniform on a 16 μm thick polyethylene terephthalate film (trade name: “G2-16” manufactured by Teijin Limited) (support). A photosensitive layer was formed by coating the film. The obtained photosensitive layer was dried at 100 ° C. for 10 minutes using a hot air convection dryer. The thickness of the photosensitive layer after drying was 50 μm.

Next, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: “NF-13”) is bonded as a protective layer on the surface of the photosensitive layer opposite to the surface in contact with the support, and the photosensitive element is attached. Obtained.

[Preparation of evaluation laminate]
Next, using a manual laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: “HLM-3000”) under the conditions of a roll temperature of 110 ° C., a laminating speed of 1.0 m / min, and a roll pressure of 0.4 MPa, While peeling off the protective layer of the photosensitive element, the photosensitive layer was pressure-bonded on the glass substrate heated at 80 ° C. for 10 minutes to obtain a laminate for evaluation.

[Evaluation of light sensitivity]
A photo tool having a stove 21-step tablet as a negative was brought into close contact with the obtained laminate for evaluation, and a stove was used by using an exposure machine manufactured by Oak Manufacturing Co., Ltd .: “EXM-1201 type”. The 21-step tablet was exposed with an energy amount such that the number of remaining steps after development was 8.0 to form a photocured portion.

Next, after peeling off the support, the photosensitive layer was developed by spraying a 1.0% by mass aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. The value of the energy amount at the time of exposure was evaluated as photosensitivity. The lower this value, the higher the photosensitivity. The results are shown in Tables 3 and 4.

[Resolution evaluation]
Lamination for evaluation: Photo tool with stove 21-step tablet and photo tool with wiring pattern with line width / space width of 30/30 to 200/200 (unit: μm) in 10 μm increments as negative for resolution evaluation It was stuck on the body. Next, using the above-described exposure machine, exposure was performed with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0, thereby forming a photocured portion.

Next, after peeling off the support, the photosensitive layer was developed by spraying a 1.0 mass% aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. Here, the smallest value (unit: μm) of the space width between the line widths in which a rectangular resist shape was obtained by development processing was evaluated as the resolution. It shows that it is excellent in the resolution, so that this value is small. The results are shown in Tables 3 and 4.

[Evaluation of tackiness]
For the evaluation laminate, the support on the laminate was peeled off without exposure, and the ease of peeling was evaluated according to the following criteria. The results are shown in Tables 3 and 4.
“A”: A polyethylene terephthalate film that can be easily peeled from the photosensitive layer.
“B”: The polyethylene terephthalate film and the photosensitive layer are slightly close to each other, but can be peeled off.
“C”: Strong adhesion between the polyethylene terephthalate film and the photosensitive layer, making it difficult to peel off.

[Evaluation of glass adhesion]
Using the exposure name “EXM-1201 type” exposure machine manufactured by Oak Manufacturing Co., Ltd. for the evaluation laminate, the amount of energy at which the number of remaining step stages after development of the stove 21-step tablet becomes 8.0 The whole surface was exposed to, and a photocured part was formed. Thereafter, a cross-cut test according to JIS-K5400 was performed, and evaluation was performed according to the following criteria. The results are shown in Tables 3 and 4.
“A”: A case where peeling is observed in an area of less than 10% of the photocured portion, or a case where peeling of the photocured portion cannot be confirmed.
“B”: A region where peeling occurs in a region of 10% or more and less than 30% of the photocured portion.
“C”: A film where peeling occurs in an area of 30% or more and less than 50% of the photocured portion.
“D”: peeling is observed in an area of 50% or more of the photocured portion.

[Evaluation of blast resistance]
A phototool having a stove 21-step tablet and a phototool having a wiring pattern with a line width / space width of 300/300 (unit: μm) as an evaluation negative were brought into close contact with each other on the evaluation laminate. Next, using the above-described exposure machine, exposure was performed with an energy amount such that the number of remaining steps after development of the stove 21-step tablet was 8.0, thereby forming a photocured portion.

Next, after peeling off the support, the photosensitive layer was developed by spraying a 1.0 mass% aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa.

Next, a sand blasting device (manufactured by Elfotec Co., Ltd., trade name: “ELP-5TR”, using SiC (silicon carbide) # 800 as an abrasive, blast pressure: 0.15 MPa, nozzle moving width: 300 mm, nozzle moving speed The resist pattern after development was sandblasted 5 times at a speed of 8 m / min and a conveyor speed of 15 mm / min, where blast resistance was evaluated according to the following criteria, and the results are shown in Tables 3 and 4 Indicated.
“A”: The resist pattern is not chipped or peeled off after sandblasting, and the line width change of the resist pattern after blasting is within 20% of the negative value.
“B”: The resist pattern is partially chipped or peeled after sand blasting, and the line width change of the resist pattern after blasting is more than 20% and 50% or less with respect to the negative value.
“C”: The resist pattern is chipped or peeled after sandblasting, and the line width change of the resist pattern after blasting exceeds 50% with respect to the negative value.

[Evaluation of peelability of resist pattern from workpiece]
Using the exposure name “EXM-1201 type” exposure machine manufactured by Oak Manufacturing Co., Ltd. for the evaluation laminate, the amount of energy at which the number of remaining step stages after development of the stove 21-step tablet becomes 8.0 The whole surface was exposed to, and a sample in which a photocured portion was formed was produced. The obtained sample was cut into a 40 mm × 50 mm rectangle. Next, after peeling off the support, the photosensitive layer was developed by spraying a 1.0% by mass aqueous sodium carbonate solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa.
The produced sample was immersed in a 3.0 mass% NaOH aqueous solution at 30 ° C., and the time for the photocured portion to peel from the glass substrate was measured and evaluated according to the following criteria. The results are shown in Tables 3 and 4.
“A”: A material that can be removed in less than 3 minutes,
“B”: 3 minutes or more and less than 5 minutes, peelable,
“C”: A material that can be peeled in 5 minutes or more and less than 10 minutes.

As is apparent from the results shown in Tables 3 and 4, Production Examples 1 to 9 are more resistant to blasting and peeling than Comparative Examples 1 to 4 which do not contain the component (b1) as the component (B). It was found to be excellent in properties and tackiness. In addition, it was found that Production Examples 1 to 9 were at least excellent in blast resistance as compared with Comparative Example 5 containing only one component (b1) as component (B). Moreover, it turned out that the manufacture example containing (E) component is further excellent in glass adhesiveness compared with the manufacture example which does not contain (E) component.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer, 16 ... To-be-processed object, 18 ... Polishing agent, 19 ... Resist pattern, 20 ... Divided object to be processed, 21 ... Photosensitive layer, 22 ... Large format glass (object to be processed), 24 ... resist pattern, 26 ... cover glass.

Claims (15)

1. (A) component: Binder polymer, (B) component: Photopolymerizable compound, (C) component: Photopolymerization initiator, (D) component: Thermoplastic compound, The said (B) component However, (b1) component: The photosensitive resin composition containing 2 or more types of different urethane (meth) acrylate containing the urethane (meth) acrylate represented by the following general formula (I).
   

   

   (In the formula, R ¹ represents a divalent organic group, and R ² represents a group represented by the following general formula (II).)
   

   

   (In the formula, R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 9 to 40.)
2. (A) component: a binder polymer, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (E) component: a silane compound having a mercapto group, The photosensitive resin composition in which B) component contains 2 or more types of different urethane (meth) acrylate containing (b1) component: Urethane (meth) acrylate represented by the following general formula (I).
   

   

   (In the formula, R ¹ represents a divalent organic group, and R ² represents a group represented by the following general formula (II).)
   

   

   (In the formula, R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 9 to 40.)
3. (A) component: Binder polymer, (B) component: a photopolymerizable compound, (C) component: a photoinitiator, The said (B) component is (b1) component: following general formula Including two (2) or more different urethane (meth) acrylates including the urethane (meth) acrylate represented by (I), the content of the component (b1) is based on the total solid content of the photosensitive resin composition A photosensitive resin composition having a content of 3 to 20% by mass.
   

   

   (In the formula, R ¹ represents a divalent organic group, and R ² represents a group represented by the following general formula (II).)
   

   

   (In the formula, R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 9 to 40.)
4. The component (B) further includes a urethane (meth) acrylate that is a reaction product of the component (b2) component: a compound having a terminal isocyanate group and a (meth) acrylate compound having a hydroxyl group,
   The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound having a terminal isocyanate group is a reaction product of a diol compound and a diisocyanate compound.
5. The photosensitive resin composition according to claim 4, wherein the component (b2) has a weight average molecular weight of 2,000 to 45,000.
6. 6. The photosensitive resin composition according to claim 4, wherein the content of the component (b2) is 20 to 50% by mass based on the total solid content of the photosensitive resin composition.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the content of the component (B) is 30 to 70% by mass based on the total solid content of the photosensitive resin composition.
8. (D) component: The photosensitive resin composition of Claim 2 or 3 which further contains a thermoplastic compound.
9. The photosensitive resin composition according to claim 1 or 8, wherein the component (D) contains an aromatic phosphate compound.
10. 10. The photosensitive resin composition according to claim 1, wherein the content of the component (D) is 1 to 20% by mass based on the total solid content of the photosensitive resin composition.
11. (E) component: The photosensitive resin composition of Claim 1 or 3 which further contains the silane compound which has a mercapto group.
12. The photosensitive resin composition according to claim 2 or 11, wherein the content of the component (E) is 0.01 to 10% by mass based on the total solid content of the photosensitive resin composition.
13. A photosensitive element comprising: a support; and a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 12 on the support.
14. A sandblast mask material formed from the photosensitive resin composition according to any one of claims 1 to 12.
15. A photosensitive layer is formed on the object to be processed using the photosensitive resin composition according to any one of claims 1 to 12, and the photosensitive layer is irradiated with actinic rays to be photocured at a predetermined position. Forming a portion, removing a portion other than the photocured portion by development to form a resist pattern, and spraying an abrasive to cut a portion of the object on which the resist pattern is not formed. A surface processing method for an object to be processed.

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