JP2011183551A - Pattern forming body and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine pattern forming body on a supporting body easily and conveniently using a dry process with good productivity and a large area by utilizing characteristics of a foaming resin layer and solving these problems. <P>SOLUTION: The pattern forming body having a concavo-convex structure is formed of the foaming resin layer on the supporting body. The pattern forming body includes a decomposable compound having a functional group for decomposing/eliminating one or more kinds of low-boiling point volatile substances by reacting with an acid or a base by an active energy ray given by the foaming resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel pattern forming body having a concavo-convex structure formed of a foamable resin layer and a method for producing the same.

The pattern forming body on the support is used as a constituent member or a process member in various fields such as electronic equipment, biotechnology, and printing. In recent years, the formation pattern has been miniaturized and used for, for example, a liquid crystal color filter, a micro flow channel chip for bio-inspection, and the like.

Conventional methods for forming various patterns such as images, circuits, and letters on a support such as a general-purpose plastic sheet or metal substrate with resin thickness or uneven structure, such as printing, photolithography, and stamping Is mentioned. In recent years, there has been a growing need for a fine pattern structure and a large area of the pattern structure, and in each method, development of a method for realizing a low cost in a short time has been promoted.

In the photolithography method described above, a desired pattern can be obtained by finally removing a resist layer irradiated with light through a photomask having a predetermined pattern with a developer. Pattern miniaturization is useful in conventional methods. However, since a large amount of developer and its cleaning solution are used, there are problems in terms of environmental protection, and a wet process is included during the process, which is complicated.

On the other hand, as the embossing method, a surface micromachining technique called microimprinting or nanoimprinting has been developed, and a pattern can be easily formed by a dry process (see, for example, Patent Document 1). However, as the desired pattern becomes finer, there is a problem that required quality such as the parallelism of the die to be embossed becomes higher, it is difficult to increase the area, and processing effort and cost are increased.

There are various printing methods. For example, the ink jet method can easily form a desired pattern and is relatively advantageous for forming a fine pattern of several tens of μm. However, it takes time to form a large area and is inferior in productivity. There are challenges. Even in the screen printing method in which large area printing is relatively advantageous, a fine pattern of 100 μm level or less is practically difficult, and various printing methods have advantages and disadvantages.

JP 2009-154393 A

As mentioned above, the current mainstream pattern forming methods such as photolithography, stamping, and printing are compatible with fine pattern formation and large area, simplicity, cost, productivity, and an environment where large amounts of chemicals are used. There was a big problem with maintainability. Therefore, an object of the present invention is to solve these problems by utilizing the characteristics of the foamable resin layer, and to provide a fine pattern formed body on a support with a large area easily and with high productivity by a dry process. That is.

The present invention includes the following aspects.
[1] A pattern forming body having a concavo-convex structure formed of a foamable resin layer on a support, and the foamable resin reacts with an acid or a base by imparting an active energy ray to thereby produce one or more low boiling points. A pattern forming body comprising a decomposable compound having a functional group capable of decomposing and desorbing a volatile substance.

[2] A method for producing a pattern forming body,
(A-1) a step of applying an active energy ray to a foamable resin layer obtained by applying a foamable resin on a support through a photomask having a pattern;
(A-2) Furthermore, the step of decomposing and desorbing the low boiling point volatile substance from the foamable resin layer by applying thermal energy;
(A-3) bonding the adhesive sheet to the foamable resin layer;
(A-4) A method for producing a pattern forming body, comprising: removing the foamable resin layer of the pattern portion provided with the active energy rays by peeling off the pressure-sensitive adhesive sheet.

[3] A method of manufacturing a pattern forming body,
(B-1) a step of bonding an adhesive sheet to a foamable resin layer obtained by applying a foamable resin on a support;
(B-2) providing an active energy ray through a photomask having a pattern;
(B-3) Furthermore, a step of decomposing and desorbing a low boiling point volatile substance from the foamable resin layer by applying thermal energy;
(B-4) A method for producing a pattern forming body, comprising: removing the foamable resin layer of the pattern portion provided with the active energy rays by peeling off the pressure-sensitive adhesive sheet.

ADVANTAGE OF THE INVENTION According to this invention, the pattern formation body which consists of a foamable resin layer from which thickness differs on a support body can be provided. In addition, it is possible to produce a large area simply and with good productivity by a dry process, and a production method excellent in productivity, cost and environmental conservation can be provided.

It is a section perspective view in one embodiment of a pattern formation object of the present invention. It is process drawing which showed one formation method of the pattern formation body of this invention. It is process drawing which showed the other formation method of the pattern formation body of this invention. It is a cross-sectional observation photograph of the test board | substrate (16) in Example 4, and a test board | substrate (17).

[Pattern formation]
FIG. 1 is a cross-sectional perspective view of an embodiment of the pattern forming body of the present invention. In the pattern forming body 1 of this embodiment, an anchor layer 20 and a foamable resin layer 30 are sequentially laminated on a support 10. The support 10 and the foamable resin layer 30 are essential, but the anchor layer 20 may be provided as appropriate in order to improve the adhesion between the support 10 and the foamable resin layer 30.

  The height of the concavo-convex structure in the pattern formed body of the present invention is not particularly limited and is appropriately adjusted depending on the application.

[Support]
The support 10 is not particularly limited as long as the foamable resin layer 30 can be molded and supported, and may be selected according to the application. When the pattern forming body is desired to have translucency, the support should also have translucency, and is not limited as long as it is appropriately adjusted by use. Examples of the support 10 include a glass substrate and a general-purpose plastic sheet, and it is preferable to select a general-purpose plastic sheet for needs that require flexibility and easy handling. Examples of the general-purpose plastic sheet include a general-purpose plastic sheet such as a polystyrene resin sheet, a polyolefin resin sheet such as polyethylene and polypropylene, and a polyester resin sheet such as polyethylene terephthalate, a polyimide resin sheet, an ABS resin sheet, and a polycarbonate resin sheet. Engineering plastic sheet.

Further, the support 10 may be subjected to a surface treatment such as a corona treatment in order to improve adhesion and fixation with the foamable resin layer 30. Moreover, you may give adhesiveness to the back surface side (side which does not shape | mold the foamable resin layer 30) of the support body 10, and is suitable when affixing on another base material simply.

[Anchor layer]
When the adhesiveness between the support 10 and the foamable resin layer 30 is not sufficient, the anchor layer 20 may be provided between them. The anchor layer 20 is a layer containing a crosslinkable compound that forms a crosslinked structure with the foamable resin layer 30.
As the crosslinkable functional group to be contained in the crosslinkable compound, for example, when a hydroxyl group is contained in the decomposable compound that is a composition component of the foamable resin layer 30, one that forms a stable crosslinked structure with the hydroxyl group is preferable. Examples thereof include an epoxy group, an isocyanate group, a methylol group, and a butyral group. The crosslinkable functional group is preferably an isocyanate group from the viewpoint of controlling the stability of the coating liquid during coating. These crosslinkable functional groups react with hydroxyl groups in the decomposable compound in the vicinity of the interface between the anchor layer 20 and the foamable resin layer 30 to form a cross-linked structure and adhere more firmly.

  Examples of the crosslinkable compound having an epoxy group include an epoxy resin and a GMA (glycidyl methacrylate) copolymer. Examples of the crosslinkable compound having a methylol group include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, and bis (2-hydroxy-3-hydroxymethyl-5-methyl). Phenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethyl-5-methylphenyl) propane, N-methylolacrylamide , Urea resin, melamine resin, phenol resin and the like.

Examples of the crosslinkable compound having a butyral group include polyvinyl butyral.

  Specific examples of the crosslinkable compound having an isocyanate group include Takenate D-110N, D-120N, D-127N, D-140N, D-160N, D-, which are XDI (xylene diisocyanate) adduct type polyisocyanates. 165N, NP1100, D-170N, D-170HN, D-172N, D-177N, D-178N, NP1200 (above, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) and the like.

  The anchor layer 20 may contain an acrylic polyol resin, an acrylic urethane resin, a (meth) acrylic resin, or the like in addition to the crosslinkable compound.

The content ratio of the crosslinkable compound in the composition of the anchor layer 20 does not impair the adhesiveness of the foamable resin layer 30, and the interface peeling occurs when the decomposable compound decomposes and desorbs the low boiling point volatile substance. Is adjusted as appropriate.

[Foaming resin layer]
The foamable resin layer 30 of the present invention contains a decomposable compound having a functional group that reacts with an acid or a base to decompose and desorb one or more low-boiling volatile substances by applying an active energy ray. It consists of things. The foamable resin layer 30 may be foamed when the low boiling point volatile substance is decomposed and desorbed. The diameter of the bubbles forming the foam structure at this time is preferably 10 μm or less when the size of the pattern to be formed is 100 μm or less, and more preferably 1 μm or less for producing a fine pattern of 10 μm or less. Moreover, when making it foam, it is preferable that the thickness of a foamable resin layer is 1 micrometer or more. The height of the concavo-convex structure formed at that time tends to be 1 μm or more.

[Decomposable compounds]
The decomposable compound of the present invention is a compound having a decomposable functional group that reacts with an acid or a base to decompose and desorb one or more low-boiling volatile substances. The low boiling point means that it has a boiling point capable of gasification at the time of decomposition / desorption (generation), that is, a boiling point lower than the temperature at the time of decomposition / desorption. The boiling point of the low-boiling volatile substance is usually 100 ° C. or lower, preferably room temperature or lower. Examples of the low boiling point volatile substance include isobutene (boiling point: −7 ° C.), carbon dioxide (boiling point: −79 ° C.), nitrogen (boiling point: −196 ° C.), and the like.

In the decomposable compound, a degradable functional group capable of generating a low boiling point volatile substance is introduced in advance. Furthermore, it is more preferable that a hydroxyl group is introduced into the decomposable compound together with the decomposable functional group in order to improve the adhesion to the anchor layer 20.

The form of the decomposable compound is not particularly limited and may be any of a monomer, an oligomer and a polymer. For example, even if it is a mixture of one or more selected from the group consisting of monomers, oligomers and polymers having a hydroxyl group and one or more selected from the group consisting of monomers, oligomers and polymers having a degradable functional group It may be a copolymer of a monomer having a hydroxyl group (hereinafter referred to as a hydroxyl group-containing monomer) and a monomer having a degradable functional group (hereinafter referred to as a degradable group-containing monomer).

  The hydroxyl group-containing monomer may be any monomer that has a hydroxyl group in the molecule and does not adversely affect the decomposition / desorption of the low boiling point volatile substance or the foaming associated therewith. Specific examples of the hydroxyl group-containing monomer are listed below, but are not limited to those exemplified. For example, glycerin monomethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, fatty acid-modified glycidyl methacrylate, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyl-oxypropyl) Ammonium chloride, 2-hydroxyethyl methacrylate (HEMA), polyethylene glycol monomethacrylate, hydroxypropyl methacrylate, polypropylene glycol monomethacrylate, poly (ethylene glycol / propylene glycol) -monomethacrylate, polyethylene glycol / polypropylene glycol / monomethacrylate, poly ( Ethylene glycol tetramethylene glycol) -monomethacrylate, poly (propylene) Propylene glycol tetramethylene glycol) - monomethacrylate, propylene glycol polybutylene glycol - monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, allyl alcohol, and the like can be used methallyl alcohol.

Among the decomposable functional groups in the decomposable group-containing monomer, those that react with an acid include a tert-butyloxy group represented by the structural formula of -O-tBu and a tert- group represented by the structural formula of -CO-O-tBu. Examples thereof include a butyloxycarbonyl group, a tert-butyl carbonate group represented by the structural formula of -O-CO-O-tBu, a keto acid, and a keto acid ester group. At this time, -tBu represents -C (CH3) 3. By reacting with an acid, tert-butyloxy and tert-butyloxycarbonyl groups are isobutene gas, tert-butyl carbonate groups are isobutene gas and carbon dioxide, keto acid sites are carbon dioxide, keto acid esters such as tert-keto acid tert -Butyloxy group generates carbon dioxide and isobutene gas. Examples of those that react with the base include urethane groups and carbonate groups. By reacting with the base, the urethane group and the carbonate group generate carbon dioxide gas.

The decomposable group-containing monomer can be classified as follows.
(1) Non-curable decomposable group-containing monomer group (2) Curable decomposable group-containing monomer group

The non-curable decomposable group-containing monomer group (1) is a degradable group-containing monomer group that does not cause a polymerization reaction even when an active energy ray is applied. The curable decomposable compound group (2) is a decomposable group-containing monomer group that undergoes a polymerization reaction upon application of active energy rays and cures, and includes a polymerizable group such as a vinyl group. . Specific examples of the decomposable group-containing monomer are listed below, but are not limited to those exemplified.

(1) -a, non-curable decomposable group-containing monomer group (acid-decomposable)
1-tert-butoxy-2-ethoxyethane, 2- (tert-butoxycarbonyloxy) naphthalene, N- (tert-butoxycarbonyloxy) phthalimide, 2,2-bis [p- (tert-butoxycarbonyloxy) phenyl] Propane etc.
(1) -b, non-curable decomposable group-containing monomer group (base decomposable)
N- (9-fluorenylmethoxycarbonyl) piperidine and the like.

(2) -a, curable decomposable group-containing monomer group (acid-decomposable)
tert-butyl acrylate, tert-butyl methacrylate, tert-butoxycarbonylmethyl acrylate, 2- (tert-butoxycarbonyl) ethyl acrylate, p- (tert-butoxycarbonyl) phenyl acrylate, p- (tert-butoxycarbonylethyl) phenyl acrylate 1- (tert-butoxycarbonylmethyl) cyclohexyl acrylate, 4-tert-butoxycarbonyl-8-vinylcarbonyloxy-tricyclo [5.2.1.02,6] decane, 2- (tert-butoxycarbonyloxy) ethyl Acrylate, p- (tert-butoxycarbonyloxy) phenyl acrylate, p- (tert-butoxycarbonyloxy) benzyl acrylate, 2- (tert Butoxycarbonylamino) ethyl acrylate, 6- (tert-butoxycarbonylamino) hexyl acrylate, p- (tert-butoxycarbonylamino) phenyl acrylate, p- (tert-butoxycarbonylamino) benzyl acrylate, p- (tert-butoxycarbonyl) Aminomethyl) benzyl acrylate, (2-tert-butoxyethyl) acrylate, (3-tert-butoxypropyl) acrylate, (1-tert-butyldioxy-1-methyl) ethyl acrylate, 3,3-bis (tert-butyloxy) Carbonyl) propyl acrylate, 4,4-bis (tert-butyloxycarbonyl) butyl acrylate, p- (tert-butoxy) styrene, m- (tert-butoxy) Styrene, p- (tert-butoxycarbonyloxy) styrene, m- (tert-butoxycarbonyloxy) styrene, acryloyl acetate, methacryloyl acetate, tert-butyl acryloyl acetate, tert-butyl methacryloyl acetate, N- (tert- Butoxycarbonyloxy) maleimide.

(2) -b, curable decomposable group-containing monomer group (base decomposability)
4-[(1,1-dimethyl-2-cyano) ethoxycarbonyloxy] styrene, 4-[(1,1-dimethyl-2-phenylsulfonyl) ethoxycarbonyloxy] styrene, 4-[(1,1-dimethyl -2-methoxycarbonyl) ethoxycarbonyloxy] styrene, 4- (2-cyanoethoxycarbonyloxy) styrene, (1,1-dimethyl-2-phenylsulfonyl) ethyl methacrylate, (1,1-dimethyl-2-cyano) Ethyl methacrylate etc.

The decomposable group-containing monomer may be used alone or in combination of two or more different types. As the decomposable compound in the present invention, it is more preferable to use a copolymer of one or more of the curable decomposable group-containing monomer group (2) and one or more hydroxyl group-containing monomers. The form of copolymerization can take any form such as random copolymerization, block copolymerization, and graft copolymerization.

Although the specific example of the decomposable compound which consists of a combination of a hydroxyl-containing monomer and two types of decomposable group containing monomers is enumerated below, it is not limited to these illustrated things.
2-hydroxyethyl methacrylate / tert-butyl acrylate / p- (tert-butoxy) styrene copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / m- (tert-butoxy) styrene copolymer, 2-hydroxyethyl Methacrylate / tert-butyl acrylate / p- (tert-butoxycarbonyloxy) styrene copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / m- (tert-butoxycarbonyloxy) styrene copolymer, 2-hydroxyethyl Methacrylate / tert-butyl methacrylate / p- (tert-butoxycarbonyloxy) styrene copolymer.

The content of the hydroxyl group-containing monomer in the decomposable compound is preferably from 5 to 60 mol%, more preferably from 10 to 40 mol%, based on the total monomer amount contained as 100 mol%. When the content of the hydroxyl group-containing monomer is 5 mol% or more, a crosslinked structure is sufficiently formed at the boundary surface between the foamable resin layer 30 and the anchor layer 20, and the adhesive strength is improved. The content of the decomposable group-containing monomer in the decomposable compound is preferably from 5 to 95 mol%, more preferably from 10 to 90 mol%, particularly preferably from 20 to 80 mol%, based on the total monomer amount contained as 100 mol%. If the content of the decomposable group-containing monomer is 5 mol% or more, a pattern in which the low-boiling volatile substance in the foamable resin layer 30 is decomposed and desorbed by the decomposition and desorption of the low-boiling volatile substance or foaming associated therewith. The portion 31 or the foamed pattern portion 32 accompanying the portion 31 can be forcibly separated from the anchor layer 20, and finally the pattern portion 31 or 32 can be easily separated by the adhesive sheet.

In addition, for the needs to improve the environmental preservation, particularly water resistance, of the foamable resin layer 30, in addition to the hydroxyl group-containing monomer and the decomposable group-containing monomer, a monomer having at least one hydrophobic functional group ( Hereinafter, a copolymer further using a hydrophobic group-containing monomer) may be used. The hydrophobic functional group is preferably selected from the group consisting mainly of an aliphatic group, an alicyclic group, an aromatic group, a halogen group, and a nitrile group.

Examples of the hydrophobic group-containing monomer include aliphatic (meth) acrylate groups such as methyl (meth) acrylate and ethyl (meth) acrylate, aromatic vinyl compound groups such as styrene, methylstyrene and vinylnaphthalene, and (meth) acrylonitrile. A compound group, a vinyl acetate compound group, a vinyl chloride compound group, etc. are mentioned. These may be used alone or in combination of two or more different types. The form of copolymerization can take any form such as random copolymerization, block copolymerization, and graft copolymerization.

Although the specific example of the decomposable compound which consists of a copolymer of a hydroxyl-containing monomer, a decomposable group containing monomer, and a hydrophobic group containing monomer is enumerated, it is not limited to what was illustrated.
2-hydroxyethyl methacrylate / tert-butyl acrylate / methyl acrylate copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / methyl methacrylate copolymer, 2-hydroxyethyl methacrylate / tert-butyl methacrylate / methyl acrylate copolymer 2-hydroxyethyl methacrylate / tert-butyl methacrylate / methyl methacrylate copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / ethyl acrylate copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / ethyl methacrylate copolymer Polymer, 2-hydroxyethyl methacrylate / tert-butyl methacrylate / ethyl acrylate copolymer 2-hydroxyethyl methacrylate / tert-butyl methacrylate / ethyl methacrylate copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / styrene copolymer, 2-hydroxyethyl methacrylate / tert-butyl acrylate / vinyl chloride copolymer 2-hydroxyethyl methacrylate / tert-butyl acrylate / acrylonitrile copolymer, 2-hydroxyethyl methacrylate / p- (tert-butoxycarbonyloxy) styrene / styrene copolymer.

The content of the hydrophobic group-containing monomer in the decomposable compound is 10 to 60 mol% when the total monomer amount used for the polymerization of the copolymer is 100 mol% from the viewpoint of environmental preservation of the foamable resin layer 30. Preferably, 20-50 mol% is more preferable. If the content of the hydrophobic group-containing monomer is 10 mol% or more, sufficient water resistance is easily obtained.

Examples of the decomposable compound having a hydrophobic functional group include a hydroxyl group-containing monomer of 5 to 60 mol%, a decomposable group-containing monomer of 20 to 85 mol%, and a hydrophobic group-containing monomer of 10 to 75 mol% (the total of these monomers is 100 mol%). ) Is preferable.

Moreover, the compound which introduce | transduced the decomposable functional group into the compound which has 1 or more types of the said hydrophobic functional group can also be used as a decomposable compound. However, the degradable functional group is easily introduced into a hydrophilic functional group selected from the group consisting mainly of a carboxylic acid group, a hydroxyl group and an amine group. Therefore, the decomposable compound is preferably a composite compound comprising a structural unit in which a degradable functional group is introduced into a hydrophilic functional group, a structural unit having a hydrophobic functional group, and a structural unit having a hydroxyl group. In particular, a vinyl copolymer is preferable.

As the decomposable compound having the hydrophobic functional group described above, one kind may be used alone, or two or more kinds may be used in combination. In this decomposable compound, the functional group composition of the compound after generating the low boiling point volatile substance contains at least one or more kinds of hydrophobic functional groups and hydroxyl groups.

In addition, organic polymer compounds such as polyether, polyamide, polyester, and polyvinyl alcohol into which a degradable functional group is introduced can also be used as the acid-decomposable or base-decomposable polymer compound. Furthermore, an acid-decomposable or base-decomposable polymer compound obtained by introducing a decomposable functional group into an inorganic compound such as silica can be used as long as the transparency is not impaired. Especially, it is preferable that a decomposable functional group is introduce | transduced into the compound group which has a functional group chosen from the group which consists of a carboxylic acid group or a hydroxyl group, and an amine group. Furthermore, a degradable functional group may be introduced into a low hygroscopic polymer material selected from the group consisting of polyester, polyimide, polyvinyl acetate, polyvinyl chloride, polyacrylonitrile, phenol resin, and dendrimer. These can be used alone as long as they have a hydroxyl group. When they do not have a hydroxyl group, they are used in combination with one or more selected from the group consisting of monomers, oligomers and polymers having a hydroxyl group. To do. The decomposable compound becomes a low hygroscopic compound after the decomposable functional group decomposes and desorbs to generate a bubble forming gas.

The decomposable compound of the foamable resin layer 30 is forcibly peeled in the vicinity of the interface between the foamable resin layer 30 and the anchor layer 20 when the low boiling point volatile substance is generated. It can be removed with an adhesive sheet. Furthermore, when the decomposable compound of the foamable resin layer 30 generates a low-boiling volatile substance, the peelability can be improved by the fine foaming of the foamable resin layer 30. That is, by removing the peeled pattern portion, a convex pattern structure composed of the foamable resin layer 30 can be formed. In order to form a fine convex pattern structure, the proportion of the structural unit derived from the hydroxyl group-containing monomer contributing to adhesiveness and the structural unit derived from the decomposable group-containing monomer contributing to peelability is appropriately adjusted. It is preferable to do.

[Acid generator and base generator]
The acid generator in the foamable resin layer 30 composition of the present invention is a compound that generates an acid by active energy rays. The base generator is a compound that generates a base by active energy rays. As the acid generator or base generator, there can be used what are called photoacid generators and photobase generators that are generally used for chemically amplified photoresists and photocationic polymerization.

As a suitable photoacid generator for the foamable resin layer 30 composition,
From (1) diazonium salt compounds, (2) ammonium salt compounds, (3) iodonium salt compounds, (4) sulfonium salt compounds, (5) oxonium salt compounds, (6) phosphonium salt compounds, etc. Mention may be made of PF _6- , AsF _6- , SbF _6- , CF ₃ SO ₃ -salts of selected aromatic or aliphatic onium compounds. Although the specific example is enumerated below, it is not limited to what was illustrated.

Bis (phenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (p-methylphenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane Bis (4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, benzoylphenylsulfonyldiazomethane, trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium Hexafluoroantimonate, 2,4,6-trimethylphenyldiphenylsulfate Nium trifluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium hexafluoro Antimonate, 1- (2-naphthoylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, (2-oxo- 1-cyclohexyl) (cyclohexyl) methylsulfonium trifluoromethanesulfonate, (2-oxo- 1-cyclohexyl) (2-norbornyl) methylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium perfluoromethanesulfonate, diphenyl-4-tert-butylphenylsulfonium perfluorooctanesulfonate, diphenyl-4-methoxyphenylsulfonium perfluoro Butanesulfonate, diphenyl-4-methylphenylsulfonium tosylate, diphenyl-4-methoxyphenylsulfonium tosylate, diphenyl-4-isopropylphenylsulfonium tosylate, diphenyliodonium, diphenyliodonium tosylate, diphenyliodonium chloride, diphenyliodonium hexafluoroarce Nate, diphenyliodonium hexa Fluorophosphate, diphenyliodonium nitrate, diphenyliodonium perchlorate, diphenyliodonium trifluoromethanesulfonate, bis (methylphenyl) iodonium trifluoromethanesulfonate, bis (methylphenyl) iodonium tetrafluoroborate, bis (methylphenyl) iodonium hexafluorophosphate Bis (methylphenyl) iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) Iodonium hexafluoroantimonate, bis (4-tert-butyl) Enyl) iodonium perfluorobutanesulfonate, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tri (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-ditrichloromethyl-1,3,5-triazine, 2- (p-methoxyphenyl) -4,6-ditrichloromethyl-1,3,5-triazine, 2-naphthyl-4 , 6-ditrichloromethyl-1,3,5-triazine, 2-biphenyl-4,6-ditrichloromethyl-1,3,5-triazine, 2- (4′-hydroxy-4-biphenyl) -4, 6-ditrichloromethyl-1,3,5-triazine, 2- (4′-methyl-4-biphenyl) -4,6-ditrichloromethyl-1,3,5-triazine, 2- (p-methoxy) Enylvinyl) -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-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -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- (3,4-Dimethoxystyrene ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,6-di-tert-butyl-4-methylpyrylium trifluoromethane Sulfonate, trimethyloxynium tetrafluoroborate, triethyloxynium tetrafluoroborate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydro Sinaphthalimide trifluoromethanesulfonate, (α-benzoylbenzyl) p-toluenesulfonate, (β-benzoyl-β-hydroxyphenethyl) p-toluenesulfonate, 1,2,3-benzenetriyltrismethanesulfonate, (2,6- Dinitrobenzyl) p-toluenesulfonate, (2-nitrobenzyl) p-toluenesulfonate, (4-nitrobenzyl) p-toluenesulfonate. Of these, iodonium salt compounds and sulfonium salt compounds are preferred.

In addition to the onium compounds, sulfonates that generate sulfonic acid upon irradiation with active energy rays, such as 2-phenylsulfonylacetophenone, halides that generate hydrogen halide upon irradiation with active energy rays, such as phenyltribromo. Methylsulfone and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and ferrocenium compounds that photogenerate phosphoric acid upon irradiation with active energy rays, such as bis (cyclopentadienyl) ferrocenium hexa Fluorophosphate, bis (benzyl) ferrocenium hexafluorophosphate, and the like can be used.

Furthermore, as an imide compound derivative having acid generating ability,
N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) ) -5-norbornene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide.

As a suitable photobase generator for the foamable resin layer 30 composition,
(1) Oxime ester compounds, (2) Ammonium compounds, (3) Benzoin compounds, (4) Dimethoxybenzyl urethane compounds, (5) Orthonitrobenzyl urethane compounds, etc. To generate an amine as a base. In addition, a base generator that generates ammonia or hydroxy ions by the action of light may be used. These include, for example, N- (2-nitropentyloxycarbonyl) piperidine, 1,3-bis [N- (2-nitrobenzyloxycarbonyl) -4-piperidyl] propane, N, N′-bis (2-nitrobenzyl). It can be selected from oxycarbonyl) dihexylamine, O-benzylcarbonyl-N- (1-phenylethylidene) hydroxylamine, and the like. Further, a compound that generates a base by heating may be used in combination with the photobase generator.

In addition, a photosensitizer may be used in combination as appropriate in order to shift or expand the wavelength region of light energy activated by the photoacid generator or photobase generator. For example, examples of photosensitizers for onium salt compounds include acridine yellow, benzoflavin, and acridine orange.

In order to minimize the amount of addition of the acid generator or base generator and light energy while generating the necessary acid, the acid proliferator and base proliferator can be used together with the acid generator or base generator. . The acid proliferator is thermodynamically stable at around room temperature, but decomposes with acid and generates a strong acid by itself to greatly accelerate the acid-catalyzed reaction. By utilizing this reaction, it is possible to improve the generation efficiency of acid or base, and to control the decomposition / desorption (generation) rate of low-boiling volatile substances and the foaming rate associated therewith. The increase in the foam generation rate gives an effect of promoting the fine foaming necessary for forming a fine pattern.

[Other resins]
The composition of the foamable resin layer 30 is preferably mixed with a general resin serving as a skeleton of the molded body in addition to the acid generator or the base generator and the decomposable compound. That is, when a non-curable monomer is used, it is difficult to mold it alone, so it is necessary to use it by mixing it with a generally used resin shown below. A general resin may be compatible or incompatible when mixed with a decomposable compound.

General resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, unsaturated polyester resins, polycarbonate resins, polyolefin resins such as polyethylene and polypropylene, polyolefin composite resins, polystyrene resins, polybutadiene resins, and (meth) acrylic resins. , Acryloyl resin, ABS (acrylonitrile / butadiene / styrene) resin, fluororesin, polyimide resin, polyacetal resin, polysulfone resin, vinyl chloride resin, methylcellulose, ethylcellulose, hydroxypropylcellulose, starch, polyvinyl alcohol, polyamide resin, phenol resin, melamine Commonly used resins such as resins, urea resins, urethane resins, epoxy resins, and silicone resins Can be used by al appropriately selected. Among the decomposable compounds, the curable low molecular weight decomposable compound group and the high molecular degradable compound group may be used alone or in combination with the generally used resins.

Whether or not the above general resin is used, other unsaturated organic compounds that are cured by active energy rays can be used in combination. Examples of combination compounds include
(1) Aliphatic, alicyclic, aromatic 1-6 valent alcohols and polyalkylene glycol (meth) acrylates (2) Aliphatic, alicyclic, aromatic 1-6 valent alcohols with alkylene (Meth) acrylates of compounds obtained by adding oxide (3) Poly (meth) acryloylalkyl phosphate esters (4) Reaction products of polybasic acid, polyol and (meth) acrylic acid (5) Reaction product of isocyanate, polyol, (meth) acrylic acid (6) Reaction product of epoxy compound and (meth) acrylic acid (7) Reaction product of epoxy compound, polyol, (meth) acrylic acid (8) Melamine and The reaction product of (meth) acrylic acid can be mentioned.

Among the compounds that can be used in combination, the curable monomer or resin can be expected to have an effect of improving physical properties such as strength and heat resistance of the foamable resin layer 30 and an effect of controlling foamability. Moreover, if a curable monomer is used for the decomposable compound and the combination compound, solvent-free molding can be performed, and a production method with less environmental load can be provided. For example, such materials are used in JP-A-8-17257 and JP-A-9-102230. Specific examples of the combined compound include methyl acrylate, ethyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclohexyl acrylate, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate , Benzylmeta Relate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxy polyethylene glycol acrylate, phenoxy polypropylene glycol acrylate, ethylene oxide modified phenoxy acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-ethylhexyl carbitol acrylate, ω-carboxypolycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid-9,10-epoxidized oleyl, ethylene maleate Glycol monoacrylate, dicyclo Pentenyloxyethylene acrylate, acrylate of caprolactone adduct of 4,4-dimethyl-1,3-dioxolane, acrylate of caprolactone adduct of 3-methyl-5,5-dimethyl-1,3-dioxolane, polybutadiene acrylate, ethylene oxide modified Phenoxylated phosphate acrylate, ethanediol diacrylate, ethanediol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol di Methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, di Tylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, neopentyl glycol diacrylate, 2-butyl-2-ethylpropanediol diacrylate, ethylene oxide modified bisphenol A diacrylate, Polyethylene oxide modified bisphenol A diacrylate, polyethylene oxide modified hydrogenated bisphenol A diacrylate, propylene oxide modified bisphenol A diacrylate, polypropylene oxide modified bisphenol A diacrylate, ethylene oxide modified isocyanuric acid diacrylate, pentaerythritol diacrylate monostearate 1,6-hexanediol diglycidyl ether acrylic acid adduct, polyoxyethylene epichlorohydrin modified bisphenol A diacrylate, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, polyethylene oxide modified trimethylolpropane triacrylate, Propylene oxide modified trimethylolpropane triacrylate, polypropylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene oxide modified isocyanuric acid triacrylate, ethylene oxide modified glycerol triacrylate, polyethylene oxide modified glycerol triacrylate, propylene oxide modified glycerol triacrylate Polypropylene oxide modified glycerol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, polycaprolactone modified Examples thereof include, but are not limited to, dipentaerythritol hexaacrylate.

Furthermore, as part or all of the combined active energy ray-curable unsaturated organic compound, an active energy ray-curable resin having a molecular weight of about 400 to 5000 having a (meth) acryloyl group at the molecular chain end can be combined. . As such a curable resin, for example, polyurethane poly (meth) acrylate polymers such as polyurethane-modified polyether poly (meth) acrylate and polyurethane-modified polyester poly (meth) acrylate are preferably used.

[Pattern formation method]
FIG. 2 is a process diagram showing one method of forming the pattern forming body 1 of the present invention. The forming method includes the following four steps.
(A-1) An active energy ray is applied to the foamable resin layer 30 obtained by applying a foamable resin on the support through the photomask 50;
(A-2) Next, by applying thermal energy to the foamable resin layer 30, the low boiling point volatile substance is decomposed and desorbed from the pattern portion 31 provided with the active energy ray,
(A-3) Furthermore, the adhesive sheet 60 is bonded to the foamable resin layer 30 side,
(A-4) By peeling off the pressure-sensitive adhesive sheet 60, the pattern portion 31 or 32 to which the active energy ray is applied is peeled off.
FIG. 3 is a process diagram showing another method for forming the pattern forming body 1 of the present invention. The forming method includes the following four steps.
(B-1) The pressure-sensitive adhesive sheet 60 is bonded to the foamable resin layer 30 obtained by applying a foamable resin on the support,
(B-2) An active energy ray is applied through the photomask 50,
(B-3) Next, by applying thermal energy to the foamable resin layer 30, the low boiling point volatile substance is decomposed and desorbed from the pattern portion 31 or 32 to which the active energy ray is applied,
(B-4) The pattern portion 31 or 32 to which the active energy ray is applied is peeled off by peeling off the adhesive sheet 60.

  The two forming methods show a process in which the pattern portion 31 in which the low boiling point volatile substance in the foamable resin layer 30 is decomposed and desorbed, or the pattern portion 32 foamed along with the decomposition and desorption is peeled and removed. However, it is not limited to these forming methods. For example, it may be a process in which a part of the pattern part 31 or 32 in the foamable resin layer 30 is peeled off in a cohesive failure state while being held on the support.

[Photomask]
The photomask 50 is formed with a pattern that shields the transmission of active energy rays. For example, as a photomask to be used on the pattern forming body, a chrome mask, a metal mask, a screen mask, a mask obtained by ion etching glass, a mask obtained by electron beam drawing of interference fringes of a planar lens having a condensing function, A transparent resin film provided with a pattern made of a substance that blocks active energy rays can be used. In order to form a fine pattern, it is preferable to apply an active energy ray by covering the photomask on the foamable resin layer 30 side (not the support side).

Moreover, the effect equivalent to a photomask is acquired by printing on the adhesive sheet which bonded the foaming resin layer 30 the ink which shields the transmittance | permeability of an active energy ray. When the active energy rays are ultraviolet rays, ordinary cyan, yellow, magenta, and black printing inks can be used. When the active energy rays have ultraviolet absorptivity, transparent printing inks may be used. . Also, so-called special color inks such as gold and silver may be used, and ultraviolet curable inks are also preferable. The printing method is not limited, and examples include letterpress printing (including flexographic printing), intaglio printing, flat plate printing (including offset printing), stencil printing (including screen printing), and plateless printing. Here, plateless printing refers to a method in which a pattern is directly formed on a substrate. Ink jet printing, which has been developed in recent years, and an electrophotographic method using dry or wet toner are known.

Moreover, a photomask can also be provided by directly printing a transparent UV curable resin containing an ultraviolet absorber on the pattern forming body 1.

[Adhesive sheet]
An adhesive sheet consists of a structure which provided the adhesion layer in the base material.

[Base material of adhesive sheet]
As the substrate, for example, coated paper such as fine paper / medium paper mainly composed of wood pulp, fine coated paper, coated paper, and art paper can be used. Further, as the substrate, plastic films such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate and polyamide, or laminated paper or synthetic paper obtained by laminating these plastics on one or both sides of paper can be used.
In particular, a transparent resin film that is transparent to visible light is more preferable because it is easy to handle when providing active energy rays. Examples of the resin constituting the transparent resin film include polystyrene, styrene-acrylic copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyetheretherketone, and triacetylcellulose.
Furthermore, non-flexible substrates can also be used as substrates, for example, glass substrates, metal substrates, and thick plastic sheets (thickness of 1 mm or more, depending on the rigidity of the substrate). Rigid base materials are mentioned. At this time, when a non-flexible substrate is also used for the support of the foamed resin layer, it becomes a peeling process between the non-flexible substrates, and generally it is difficult to peel off by applying an external force. Then, the low boiling point volatile substance is easily decomposed and desorbed from the foamable resin layer between the non-flexible substrates, and the peelability can be improved by reducing the close contact between the substrates.

[Adhesive layer of adhesive sheet]
An adhesion layer is a layer which has adhesiveness, and consists of a coating film of various adhesives or an adhesive. Examples of the adhesive include casein, soybean protein, synthetic protein, starches such as starch and oxidized starch, polyvinyl alcohols such as polyvinyl alcohol, cationic polyvinyl alcohol, modified polyvinyl alcohol such as silyl-modified polyvinyl alcohol, carboxymethylcellulose, Cellulose derivatives such as methyl cellulose, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylic copolymer, vinyl acetate copolymer, latex of vinyl polymer such as ethylene-vinyl acetate copolymer or Examples thereof include a solution, an aqueous polyurethane resin, and an aqueous polyester resin.

The pressure-sensitive adhesive is appropriately selected from, for example, various known rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, etc., but from the viewpoint of pressure-sensitive adhesive performance, an acrylic pressure-sensitive adhesive mainly composed of a polyacrylate ester. Agents are preferred. The pressure-sensitive adhesive may be water-based, emulsion-based, solvent-based, solvent-free, or hot-melt-based, but an emulsion-based or solvent-based one is preferable from the viewpoint of adhesive performance.
The pressure-sensitive adhesives are classified into a strong pressure-sensitive adhesive type, a general-purpose type, and a weak pressure-sensitive adhesive type according to the adhesive strength, and those having an adhesive level according to the application can be appropriately selected.

The adhesive or pressure-sensitive adhesive may contain a cross-linking agent as necessary. Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, butylated melamine compounds, and the like. Among these crosslinking agents, an isocyanate compound and an epoxy compound are preferable because the acrylic polymer can be easily crosslinked.
Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Examples thereof include glycidyl ether, tetraglycidyl xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, sorbitol polydiglycidyl ether, and the like. The content of the crosslinking agent is preferably selected as appropriate according to the desired pressure-sensitive physical properties.

The adhesive or pressure-sensitive adhesive may contain other additives such as a tackifier, a silane coupling agent, a UV absorber, a light stabilizer such as a hindered amine compound, and a filler as necessary. Good. Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, and petroleum resin.
Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds.

[Adhesion sheet bonding and peeling method]
The method for laminating and peeling the adhesive sheet on the foamable resin layer 30 can be selected from general-purpose methods. As a bonding method, it can bond together with a pressure roller or a press, for example. Furthermore, in order to raise the adhesiveness of an adhesive sheet, it can also bond together, heating.

Hereinafter, the present invention will be described according to examples. However, the present invention is not limited to these.
Unless otherwise indicated, parts and% indicate parts by mass and mass% in terms of solid content.

[Example 1]
(Anchor layer formation process)
As the support, Cosmo Shine A4300 (thickness 125 μm), which is a PET (polyethylene terephthalate) film manufactured by Toyobo Co., Ltd., was used.
Also, Takenate D-110N (Mitsui Chemicals Polyurethane Co., Ltd.) (1 part) and Mobital B60HH (Kuraray Co., Ltd.) (9 parts) were mixed, and these were mixed with 2-butanone (methyl ethyl ketone) and a non-volatile component of 9.0% by mass. To prepare an anchor layer coating material A.
Next, the anchor layer coating material A is applied onto the support using a wire bar so that the nonvolatile component is 0.7 g / m ^2, and dried (130 ° C., 1 minute) to form an anchor layer. The test substrate (1) was obtained.

(Foaming resin layer formation process)
As the decomposable compound, a copolymer of tert-butyl methacrylate (38 mol%), methyl methacrylate (36 mol%), 2-hydroxyethyl methacrylate (20 mol%) and n-butyl methacrylate (6 mol%) was used. Moreover, 2- [2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) -pentyl] which is an onium salt acid generator as an acid generator -Fluorene (CGI-1907, manufactured by Ciba Japan) was used.
As the composition of the foamable resin layer, the decomposable compound (100 parts) and the acid generator (0.5 part) are mixed, and these are mixed with ethyl acetate for a foamable resin layer having a nonvolatile component of 25.0% by mass. Paint B was obtained.
Then, using an applicator bar (doctor blade, manufactured by Yoshimitsu Seiki Co., Ltd.) with a gap of 160 μm, the foamable resin layer coating material B was applied onto the anchor layer of the test substrate (1) and dried (105 ° C., 8 minutes), a foamable resin layer was formed to obtain a test substrate (2). The thickness of the foamable resin layer was 20 μm.

(Adhesion sheet bonding process)
The used adhesive sheet was produced by the following method. A PET film G2 (thickness 75 μm) manufactured by Teijin DuPont was used as a support.
As an adhesive component, 100 parts by mass of SH101 (manufactured by Toyo Ink Co., 60%) as the main agent and 2 parts by mass of BXX6105 (manufactured by Toyo Ink Co., Ltd., 37.5%) as a curing agent are mixed, and an adhesive paint D was obtained.
Next, using the applicator bar with a gap of 100 μm, the adhesive paint D was applied onto the PET film G2, dried (100 ° C., 2 minutes), and left at room temperature for 1 week to obtain an adhesive sheet. . The thickness of the adhesive layer was 12 μm.
The produced adhesive sheet was bonded to the foamable resin layer of the test substrate (2) using a laminator to obtain a test substrate (3).

(UV irradiation process)
A test substrate (4) was obtained by exposing the test substrate (3) to ultraviolet rays while using a vacuum exposure machine to bring the mask pattern into close contact with the base material side of the adhesive sheet. Ultraviolet rays were irradiated using a metal halide lamp (ultraviolet curing multi-metal lamp M03-L31, manufactured by Eye Graphics Co., Ltd.) as a light source so that the irradiation amount was 300 mJ / cm ² .

(Heating process)
The test substrate (4) was heat-treated for 2 minutes with a constant temperature dryer at 130 ° C. A test substrate (5) in which the irradiated pattern portion was foamed was obtained.
(Adhesive sheet removal process)
The adhesive sheet was removed from the test substrate (5) to obtain a test substrate (6) from which the foamed pattern was removed. The foamed portion of the foamable resin layer corresponding to the pattern was removed, and a pattern formed body could be produced.

[Example 2]
A test substrate (7) similar to the test substrate (3) of Example 1 was prepared, and UV curable ink (UV-manufactured by Toyo Ink Co., Ltd.) was applied to the base material of the adhesive sheet of the test substrate (7) by offset printing. OP varnish) is printed so as to form an ultraviolet shielding layer having a thickness of 1 μm, and 300 mJ / cm ² of ultraviolet rays are applied from the side on which the ultraviolet shielding layer is formed, using an ultraviolet irradiation device provided in advance in an offset printer. Irradiation gave a test substrate (8).
By irradiating with ultraviolet rays, the ultraviolet curable ink is cured, and ultraviolet rays are applied only to the unprinted portion of the test substrate (7). The test substrate (8) was further subjected to a heating step and a pressure-sensitive adhesive sheet removal step in the same manner as in Example 1 to produce a pattern formed body.

[Example 3]
An anchor layer was not provided, and the foaming resin layer forming step was performed in the same manner as in Example 1 to obtain a test substrate (9). Then, the pattern formation body was produced in the following processes.
(UV irradiation process)
A test substrate (10) was obtained by irradiating the test substrate (9) with ultraviolet rays while adhering a mask pattern to the foamable resin layer side using a vacuum exposure machine.
(Heating process)
The test substrate (11) foamed to the irradiated pattern was obtained by removing the mask pattern of the test substrate (10) and performing heat treatment for 2 minutes in a constant temperature dryer at 130 ° C.

(Adhesion sheet bonding process)
The pressure-sensitive adhesive sheet produced in the same manner as in Example 1 was bonded to the foamable resin layer of the test substrate (11) using a laminator to obtain a test substrate (12).
(Adhesive sheet removal process)
The adhesive sheet was removed from the test substrate (12) to obtain a test substrate (13) from which the foamed pattern was removed. The pattern foaming part of the foamable resin layer corresponding to the pattern was removed, and a pattern formed body could be produced.

[Example 4]
In the foamable resin layer forming step of Example 1, the test substrate (14) was obtained in the same manner except that the nonvolatile component of the foamable resin layer coating material B was adjusted to 27.5% instead of 25.0% by mass. It was. The thickness of the foamable resin layer was 25 μm. Then, it exposed by irradiating with an ultraviolet-ray, making a mask pattern closely_contact | adhere to the foaming resin layer side of the said test board | substrate (14), and obtained the test board | substrate (15). The ultraviolet light source was the same as in Example 1, and the irradiation amount was 100 mJ / cm ² .
Thereafter, the test substrate (15) was heat-treated for 2 minutes with a constant temperature dryer at 150 ° C. A test substrate (16) in which the irradiated pattern portion was foamed was obtained. A photograph of the cross section of the test substrate (16) observed with an optical microscope is shown in FIG. 4-1.
The test substrate (16) is foamed by removing the adhesive sheet after adhering the adhesive sheet (Oji Tack; using OPT1, PET base material) to the foamable resin layer side at 70 ° C. with a metal press. A test substrate (17) from which the pattern was removed was obtained. The foamed portion of the foamable resin layer corresponding to the pattern was removed, and a pattern formed body having a convex shape with a width of 60 μm and a height of 30 μm could be produced. A photograph of the cross section of the test substrate (17) observed with an optical microscope is shown in FIG. 4-1.

[Comparative Example 1]
In the foamable resin layer forming step of Example 1, the same procedure as in Example 1 was performed except that polymethyl methacrylate (PMMA) was used instead of the decomposable compound.

[Comparative Example 2]
In the foamable resin layer forming step of Example 4, the same procedure as in Example 4 was performed except that polymethyl methacrylate (PMMA) was used instead of the decomposable compound.

From Example 1 to Example 4, the portion of the foamable resin layer not provided with the active energy ray does not peel at all, and only the pattern portion provided with the active energy ray is completely peeled off from the foamable resin layer. The pattern formation body which can be produced.
On the other hand, in Comparative Example 1 and Comparative Example 2, since the low boiling point volatile substance cannot be decomposed and desorbed from polymethyl methacrylate, the pattern portion provided with the active energy ray is not peeled off, and a predetermined pattern forming body is produced. could not.

DESCRIPTION OF SYMBOLS 1 Pattern formation body 10 Support body 20 Anchor layer 30 Foamable resin layer 31 The pattern part 32 in which the low boiling point volatile substance decomposed | disassembled in the foamable resin layer 30, and the low boiling point volatile substance was separated in the foamable resin layer 30 The pattern portion 50 that has been desorbed and desorbed and foamed as a result of the decomposition and desorption is provided. Photomask 60 Adhesive sheet

Claims (4)

  A pattern forming body having a concavo-convex structure formed by a foamable resin layer on a support, wherein the foamable resin gives an active energy ray to react with an acid or a base and one or more low boiling point volatile substances A pattern-forming body comprising a decomposable compound having a functional group capable of decomposing and desorbing a compound. A method for producing a pattern formed body, comprising:
(A-1) a step of applying an active energy ray to a foamable resin layer obtained by applying a foamable resin on a support through a photomask having a pattern;
(A-2) Furthermore, the step of decomposing and desorbing the low boiling point volatile substance from the foamable resin layer by applying thermal energy;
(A-3) bonding the adhesive sheet to the foamable resin layer;
(A-4) A method for producing a pattern forming body, comprising: removing the foamable resin layer of the pattern portion provided with the active energy rays by peeling off the pressure-sensitive adhesive sheet. A method for producing a pattern formed body, comprising:
(B-1) a step of bonding an adhesive sheet to a foamable resin layer obtained by applying a foamable resin on a support;
(B-2) providing an active energy ray through a photomask having a pattern;
(B-3) Furthermore, a step of decomposing and desorbing a low boiling point volatile substance from the foamable resin layer by applying thermal energy;
(B-4) A method for producing a pattern forming body, comprising: removing the foamable resin layer of the pattern portion provided with the active energy rays by peeling off the pressure-sensitive adhesive sheet.   The manufacturing method of the pattern formation body whose base material of the adhesive sheet of Claim 3 is an inflexible base material.

Images