WO2011052461A1 - 表面に3次元模様を有するポリマーシートの製造方法 - Google Patents
表面に3次元模様を有するポリマーシートの製造方法 Download PDFInfo
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- WO2011052461A1 WO2011052461A1 PCT/JP2010/068540 JP2010068540W WO2011052461A1 WO 2011052461 A1 WO2011052461 A1 WO 2011052461A1 JP 2010068540 W JP2010068540 W JP 2010068540W WO 2011052461 A1 WO2011052461 A1 WO 2011052461A1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
Definitions
- the present invention relates to a method for producing a polymer sheet having a three-dimensional pattern on the surface.
- polymer sheets have been used in various applications (for example, applications such as table cloths, flooring materials, and wallpaper).
- applications such as table cloths, flooring materials, and wallpaper
- a three-dimensional pattern may be formed on the surface from the viewpoint of improving the design.
- the polymer sheet is pressed against a mold, a sheet, a roll, or the like provided with a concavo-convex shape and thermally deformed, thereby forming a concavo-convex shape on the polymer sheet surface
- Patent Document 1 a forming form for transferring the material
- Patent Document 2 A polymer member in which an incompatible substance is unevenly distributed is known (see Patent Document 2).
- This polymer member is provided with irregularities on the surface by paying attention to the phenomenon that the incompatible substance is segregated on the surface when a polymerizable composition containing the incompatible substance is applied onto the monomer absorption layer.
- the unevenness on the surface depends on the shape and size of the incompatible material, and in order to form the uneven shape on the surface, the fine particles are dispersed in the polymerizable composition as the incompatible material. It was limited to the case.
- an object of the present invention is to provide a method by which a polymer sheet having a three-dimensional pattern on the surface can be produced by a simple method.
- a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof on one side of the polymer sheet is an essential component.
- a polymer sheet having a three-dimensional pattern on the surface simply by coating the polymerizable composition, changing the surface shape of the surface on which the polymerizable composition is applied three-dimensionally, and then curing by polymerization. The present invention was completed.
- a polymerizable composition containing a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof is applied as a surface.
- a method for producing a polymer sheet having a three-dimensional pattern on a surface, wherein the shape is three-dimensionally changed and then cured by polymerization to form a three-dimensional pattern on the surface is provided.
- the present invention comprises applying a polymerizable composition containing, as an essential component, a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof on one side of the polymer sheet,
- a polymerizable composition containing, as an essential component, a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof on one side of the polymer sheet.
- a method for producing a polymer sheet having the above-mentioned three-dimensional pattern wherein the time from application of the polymerizable composition on one side of the polymer sheet to polymerization is one minute or longer.
- a method for producing a polymer sheet having a three-dimensional pattern wherein the polymerizable composition further contains a substance that is not absorbed by at least one polymer sheet.
- a method for producing a polymer sheet having a three-dimensional pattern wherein either or both of the polymer sheet and the polymerizable composition contain a photopolymerization initiator.
- a method for producing a polymer sheet having the three-dimensional pattern that is polymerized and cured by irradiation with active energy rays is provided.
- a method for producing a polymer sheet having the three-dimensional pattern in which the active energy ray is ultraviolet light is provided.
- the polymer sheet having a three-dimensional pattern on the surface can be easily produced because of the above-described configuration.
- FIG. 2 is a scanning electron micrograph showing a partial cross section of Example 1.
- FIG. 2 is a scanning electron micrograph showing a part of the surface of Example 1.
- FIG. 2 is a scanning electron micrograph showing a part of the surface of Example 2.
- FIG. 4 is a scanning electron micrograph showing a part of the surface of Example 3.
- FIG. 6 is a scanning electron micrograph showing a part of the surface of Example 4.
- FIG. 6 is a scanning electron micrograph showing a part of the surface of Example 5.
- FIG. 6 is a scanning electron micrograph showing a part of the surface of Example 5.
- FIG. 6 is a scanning electron micrograph showing a partial cross section of Example 5.
- FIG. 6 is a scanning electron micrograph showing a partial cross section of Example 5.
- FIG. 10 is a photograph showing the surface of Example 5.
- 6 is a scanning electron micrograph showing the surface of Example 6.
- FIG. 6 is a scanning electron micrograph showing a partial cross section of Example 6.
- FIG. 10 is a photograph
- a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof is provided on one side of the polymer sheet.
- a polymer sheet having a three-dimensional pattern is obtained by applying a polymerizable composition as an essential component, changing the surface shape three-dimensionally, and then curing by polymerization to form a three-dimensional pattern on the surface. Can do.
- sheet includes a tape-shaped material, that is, a “tape”.
- the coating layer of the polymerizable composition formed by applying the polymerizable composition on one side of the polymer sheet may be referred to as a “polymerizable composition coating layer”.
- the “method for producing a polymer sheet having a three-dimensional pattern on the surface of the present invention” may be simply referred to as “the method for producing the present invention”.
- a polymerizable composition containing at least one kind of polymerizable monomer that can be absorbed by the polymer sheet or a partial composition thereof as an essential component is applied to at least one side of the polymer sheet.
- a step of three-dimensionally changing the surface shape of the surface coated with the polymerizable composition [step (i)], a step of forming a three-dimensional pattern on the surface by applying the polymerization [step (ii) ]
- step (ii) As an essential step.
- the polymer sheet is a sheet composed of a single polymer layer, and can absorb at least one of the polymerizable monomers of the polymerizable composition from the polymerizable composition. That is, the “polymer sheet” referred to in the present application refers to a sheet-shaped or film-shaped polymer that acts as a monomer absorption layer.
- the monomer absorption layer is a layer that can interact with at least one of the polymerizable monomers, suck the polymerizable monomer, and move it to the inside of the layer (can be taken into the layer). Layer).
- the surface provided by the monomer absorption layer is a surface that absorbs the polymerizable monomer, that is, a monomer absorption surface.
- the polymer sheet may exist as a monomer absorption layer provided on at least one surface side of a support body (support body for polymer sheet) described later. That is, the polymer sheet may be a monomer absorption layer in a laminated sheet composed of a polymer sheet and a support described later.
- a laminated sheet is advantageous in terms of handleability and workability.
- the polymer sheet In the relationship between the polymer sheet and the polymerizable monomer, whether or not the polymer sheet corresponds to the monomer absorption layer for the polymerizable monomer is determined depending on whether or not the following condition is satisfied.
- the weight of the polymer sheet becomes more than twice the initial weight, and the polymer sheet is excessive.
- the weight of the polymer sheet becomes twice or more of the initial weight without disappearing by dissolution when immersed in a polymerizable monomer in an amount (at least 300 times the weight of the polymer sheet) at 25 ° C. for 3 days It is judged by.
- the polymer sheet when this condition is satisfied, that is, when the weight of the polymer sheet is more than twice the initial weight in both cases, in the present invention, the polymer sheet is the polymerized polymer.
- the polymer sheet as the monomer absorption layer can be formed using a known / conventional method.
- a support polymer sheet support
- a release of a separator is used.
- a composition for forming a polymer sheet as a monomer absorption layer is applied, and if necessary, dried. It can be formed by performing polymerization or the like.
- the composition which forms the polymer sheet (polymer layer as a monomer absorption layer) as a monomer absorption layer may be called "monomer absorption layer formation composition".
- the monomer-absorbing layer forming composition is not particularly limited.
- a monomer-absorbing layer-forming composition containing a polymer as an essential component, a monomer mixture (monomer mixture) forming a polymer, or a monomer containing a partial polymer thereof as an essential component examples include an absorbent layer forming composition.
- the former includes, for example, a so-called solvent-type monomer absorption layer forming composition, and the latter includes, for example, a so-called active energy ray-curable monomer absorption layer forming composition.
- a crosslinking agent and other various additives may be used for the monomer absorption layer forming composition as needed.
- the polymer constituting the polymer sheet is not particularly limited as long as it can absorb at least one of the polymerizable monomers that are the components of the polymerizable composition.
- an acrylic polymer, a rubber polymer, a vinyl alkyl ether polymer, A silicone polymer, a polyester polymer, a polyamide polymer, a urethane polymer, a fluorine polymer, an epoxy polymer, and the like can be appropriately selected and used.
- acrylic polymers are particularly preferred from the viewpoints of a wide selection range of monomers that can be absorbed, a wide range of mechanical properties such as strength and softness, and excellent transparency and weather resistance.
- the polymer sheet that is the monomer absorption layer is preferably an acrylic polymer sheet.
- the said polymer can be used individually or in combination of 2 or more types.
- the polymer sheet as the monomer absorption layer may be a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) having the above polymer as a base polymer.
- the pressure-sensitive adhesive forming such a pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives. Examples thereof include an adhesive, a fluorine-based adhesive, and an epoxy-based adhesive. That is, the polymer sheet that is the monomer absorption layer may be an adhesive sheet (pressure-sensitive adhesive sheet).
- the polymer sheet is an adhesive layer
- the polymer sheet having a three-dimensional pattern on the surface obtained by the production method of the present invention can exhibit adhesiveness.
- an acrylic polymer having a (meth) acrylic acid ester as a monomer component particularly an acrylic polymer in which the main monomer component (monomer main component) is a (meth) acrylic acid alkyl ester is preferably used.
- (meth) acrylic acid alkyl ester include (meth) acrylic acid alkyl ester having a linear or branched alkyl group and (meth) acrylic acid alkyl ester having a cyclic alkyl group.
- said "(meth) acryl” represents "acryl” and / or "methacryl", and others are the same.
- (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.
- Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.
- (meth) acrylic acid alkyl esters having 1 to 14 carbon atoms in the alkyl group are preferable, and (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms in the alkyl group are more preferable.
- Examples of the (meth) acrylic acid alkyl ester having a cyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
- the ratio of the (meth) acrylic-acid alkylester is the monomer component whole quantity for forming an acrylic polymer, for example It is important that the amount is 60% by weight or more (preferably 80% by weight or more).
- various copolymerizable monomers such as polar group-containing monomers and polyfunctional monomers may be used as monomer components.
- a copolymerizable monomer as the monomer component, for example, the cohesive force can be increased.
- a copolymerizable monomer can be used individually or in combination of 2 or more types.
- Examples of the polar group-containing monomer include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid or anhydrides thereof (such as maleic anhydride); Hydroxyl-containing monomers such as hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N, N-dimethyl (meth) acrylamide, Amide group-containing monomers such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Meta Amino group-containing monomers such as t-butylaminoeth
- the amount of the polar group-containing monomer used is 30% by weight or less (for example, 1 to 30% by weight), preferably 3 to 20% by weight, based on the total amount of monomer components for forming the acrylic polymer.
- the usage-amount of a polar group containing monomer exceeds 30 weight%, cohesion force will become high too much, for example, a malfunction may be produced in the point of a softness
- there is too little usage-amount of a polar group containing monomer for example, it is less than 1 weight% with respect to the monomer component whole quantity for forming an acrylic polymer
- the handling as a polymer sheet may be difficult.
- polyfunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl.
- the amount of the polyfunctional monomer used is 20% by weight or less (for example, 0.01 to 20% by weight), preferably 0.02 to 1% by weight, based on the total amount of monomer components for forming the acrylic polymer. %. If the amount of the polyfunctional monomer used exceeds 20% by weight based on the total amount of the monomer components for forming the acrylic polymer, for example, the cohesive force of the acrylic polymer becomes too high and the monomer absorbability may be impaired. . In addition, when the amount of the polyfunctional monomer used is too small (for example, less than 0.01% by weight based on the total amount of monomer components for forming the acrylic polymer), for example, the cohesive strength of the acrylic polymer is reduced. Or may be dissolved in the polymerizable monomer.
- copolymerizable monomers other than polar group-containing monomers and polyfunctional monomers examples include vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; ethylene, butadiene, and isoprene. And olefins or dienes such as isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride and the like.
- the polymer constituting the polymer sheet as the monomer absorption layer is not particularly limited, but a polymer having at least one of the polymerizable monomers of the polymerizable composition described below as a structural unit is preferable. This is because if the structural unit is common, the polymerizable monomer is more easily absorbed into the polymer sheet, and a three-dimensional pattern on the surface is more easily formed.
- the polymerizable composition is preferably an acrylic monomer mixture having an acrylic monomer as a main monomer or a polymerizable acrylic composition having a partial polymer thereof as an essential component
- the polymer sheet has such a point. Therefore, an acrylic polymer sheet (acrylic polymer layer) is preferable.
- the above acrylic polymer can be prepared by polymerizing (copolymerizing) monomer components by a known or conventional polymerization method.
- a polymerization method include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method by irradiation with active energy rays (an active energy ray polymerization method, a photopolymerization method), and the like.
- the active energy ray polymerization method is preferable because energy saving and a relatively thick polymer layer (polymer sheet) can be easily obtained without using an organic solvent, and an ultraviolet polymerization method by ultraviolet irradiation is particularly preferable.
- a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator can be used depending on the type of the polymerization reaction.
- the monomer-absorbing layer-forming composition preferably contains a photopolymerization initiator.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- the photopolymerization initiator is not particularly limited.
- benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime.
- a photopolymerization initiator, a benzoin photopolymerization initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, or the like can be used.
- a photoinitiator can be used individually or in combination of 2 or more types.
- the ketal photopolymerization initiator includes, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one [for example, trade name “Irgacure 651” (manufactured by Ciba Japan)] Etc. are included.
- examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [for example, trade name “Irgacure 184” (manufactured by Ciba Japan)], 2,2-diethoxyacetophenone, 2,2-dimethoxy- Examples include 2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
- acylphosphine oxide photopolymerization initiator for example, trade name “Lucirin TPO” (manufactured by BASF) can be used.
- ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. .
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
- Examples of the benzoin photopolymerization initiator include benzoin.
- Examples of the benzyl photopolymerization initiator include benzyl.
- benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
- the amount of the photopolymerization initiator used is not particularly limited. For example, 0.01 to 5 parts by weight (preferably 0.05 to 3 parts by weight) with respect to 100 parts by weight of all monomer components forming the acrylic polymer. ) Can be selected from the range.
- Examples of the active energy rays used in the polymerization method by irradiation with the active energy rays include ionizing radiations such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, and ultraviolet rays, and particularly ultraviolet rays. Is preferred.
- the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause a polymerization reaction.
- thermal polymerization initiator examples include azo polymerization initiators [for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′- Azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'- Dimethyleneisobutylamidine) dihydrochloride, etc.], peroxide-based polymerization initiators (for example, dibenzoyl peroxide, tert-butylpermaleate).
- azo polymerization initiators for example, 2,2′-azobisisobutyronitrile
- Redox polymerization initiators such as organic peroxide / vanadium compound; the organic peroxide / dimethylaniline; naphthenic acid metal salt / butyl aldehyde, a combination such as aniline or acetylbutyrolactone, and the like.
- the amount of the thermal polymerization initiator used is not particularly limited as long as it can be used as a thermal polymerization initiator. If a redox polymerization initiator is used as a thermal polymerization initiator, it can be polymerized at room temperature.
- a known and commonly used organic solvent can be used.
- ester solvents such as ethyl acetate and methyl acetate
- ketone solvents such as acetone and methyl ethyl ketone
- alcohol solvents such as methanol, ethanol and butanol
- hydrocarbon solvents such as cyclohexane, hexane and heptane
- toluene and xylene Aromatic solvents can be used.
- These organic solvents may be used alone or in combination of two or more.
- a crosslinking agent may be added to the monomer-absorbing layer forming composition.
- the crosslinking agent an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, A carbodiimide type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, an amine type crosslinking agent, etc. are mentioned. Among these, from the viewpoint of handleability, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are preferable.
- a crosslinking agent can be used individually or in combination of 2 or more types.
- isocyanate crosslinking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone.
- Alicyclic polyisocyanates such as diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
- Aromatic polyisocyanates and the like, and other trimethylolpropane / tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., Name "Coronate L”], trimethylolpropane / hexamethylene diisocyanate adduct [Nippon Polyurethane Industry Co., Ltd. under the trade name "Coronate HL”], and the like are also used.
- epoxy-based crosslinking agent examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1 , 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyg In addition to sidyl ether, a
- the monomer-absorbing layer forming composition may contain appropriate additives as necessary.
- additives include surfactants (for example, ionic surfactants, silicone surfactants, fluorosurfactants, etc.), tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum Resin, oil-soluble phenol resin, etc., which are solid, semi-solid or liquid at normal temperature), plasticizers, fillers, anti-aging agents, antioxidants, colorants (pigments, dyes, etc.).
- the amount of these additives can be appropriately selected within a range not impairing the effects of the present invention.
- the monomer-absorbing layer-forming composition is the same as or similar to the polymerizable composition described below from the viewpoint of ease of forming a three-dimensional surface pattern and workability associated with the ease of migration of the polymerizable monomer. It preferably has a composition.
- the monomer-absorbing layer-forming composition has a composition that approximates the polymerizable composition
- a monomer-absorbing layer-forming composition having at least one polymerizable monomer as a forming component
- a monomer having at least one polymerizable monomer of the polymerizable composition and a partial structure characterizing the monomer for example, an acrylate structure portion of an acrylic monomer, an epoxy structure portion of an epoxy monomer, etc.
- a monomer absorption layer forming composition for example, an acrylate structure portion of an acrylic monomer, an epoxy structure portion of an epoxy monomer, etc.
- the monomer absorption layer forming composition has an acrylic monomer absorption that forms an acrylic polymer. It is preferable that it is a layer forming composition.
- the method for forming the polymer sheet as the monomer absorption layer is not particularly limited, and a known / conventional method can be appropriately selected.
- the monomer absorption layer forming composition (such as a monomer absorption layer forming composition solution) containing an acrylic polymer as an essential component
- the monomer absorption layer forming composition is placed on a predetermined surface (for example, the following (On at least one side of the support for the polymer sheet) so that the thickness after drying is a predetermined thickness, and drying and / or curing as necessary (direct copying method), suitable
- a predetermined surface for example, the following (On at least one side of the support for the polymer sheet) so that the thickness after drying is a predetermined thickness, and drying and / or curing as necessary (direct copying method), suitable
- the monomer-absorbing layer-forming composition is applied onto the release liner so that the thickness after drying becomes a predetermined thickness, and dried and / or cured as necessary, a polymer sheet is formed, and then the polymer sheet And the like (for example, at least one side of the following support for polymer sheets) or the like (transfer method).
- a monomer absorption layer formation composition which has the mixture (monomer mixture) of the monomer component which forms an acryl-type polymer, or its partial polymerization component as an essential component
- a monomer absorption layer formation composition is on a predetermined surface (for example, , Coating on at least one surface of the following support for polymer sheet, etc.), irradiating active energy rays, and forming polymer sheets by curing active energy rays (direct copying method), on an appropriate release liner
- the polymer sheet is formed on a predetermined surface (for example, at least of the following support for polymer sheets). For example, a method of transferring (transferring) to a surface on one side (transfer method) or the like can be given. Furthermore, you may add a drying process as needed.
- a method of forming a polymer sheet by active energy ray curing is preferable because a relatively thick polymer sheet can be obtained without using an organic solvent with energy saving.
- a conventional coater for example, a comma roll coater, a die roll coater, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a sprayer
- a coater or the like For example, a comma roll coater, a die roll coater, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a sprayer
- the polymerizable composition coating layer (on one side of the polymer sheet) is used because of the ease of forming a three-dimensional pattern.
- the ratio of the polymerizable composition layer immediately after coating) / polymer sheet formed by coating the polymerizable composition is preferably 0.51 to 100, and more preferably 1 to 50. If the ratio is less than 0.51, a three-dimensional pattern is not formed, and if it exceeds 100, the three-dimensional pattern does not appear on the surface.
- the specific thickness is preferably 1 to 1000 ⁇ m, preferably 2 to 500 ⁇ m, and particularly preferably 5 to 200 ⁇ m from the viewpoint of handleability.
- the polymer sheet as the monomer absorption layer may be provided on at least one surface side of the support (support for polymer sheet).
- the support (support for polymer sheet) As the body for example, a paper-based support such as paper; a fiber-based support such as cloth, non-woven fabric, or net; a metal-based support such as metal foil or metal plate; a plastic support such as a plastic film or sheet A rubber-based support such as a rubber sheet; a foam such as a foam sheet; and a laminate thereof [for example, a laminate of a plastic-based support and another support, or a laminate of plastic films (or sheets). Etc.] can be used.
- a plastic support such as a plastic film or sheet can be suitably used.
- ⁇ -olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and the like are used as monomers.
- Olefin resin Polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyvinyl chloride (PVC); vinyl acetate resin; polyphenylene sulfide (PPS); polyamide ( Nylon), amide resins such as wholly aromatic polyamide (aramid); polyimide resins; polyetheretherketone (PEEK). These materials can be used alone or in combination of two or more.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PVC polyvinyl chloride
- PPS vinyl acetate resin
- PPS polyphenylene sulfide
- polyamide Nylon
- amide resins such as wholly aromatic polyamide (aramid)
- polyimide resins polyetheretherketone (PEEK).
- the deformability such as elongation may be controlled by a stretching process or the like.
- a support body when a polymer sheet is formed by hardening by an active energy ray, it is preferable to use what does not inhibit permeation of an active energy ray.
- the surface of the support is chemically or physically treated with conventional surface treatments such as corona treatment, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion to the polymer layer.
- the method may be subjected to oxidation treatment or the like, or may be subjected to coating treatment with a primer or a release agent.
- the thickness of the support can be appropriately selected according to the strength, flexibility, purpose of use, and the like. For example, it is generally 1000 ⁇ m or less (for example, 1 to 1000 ⁇ m), preferably 1 to 500 ⁇ m, more preferably 3 to Although it is about 300 micrometers, it is not limited to these.
- the support may have any form of a single layer or a laminate.
- a third layer may be provided between the polymer sheet and the support.
- the third layer include an adhesive layer for the purpose of enhancing adhesiveness, and a conductive layer that imparts antistatic properties.
- the polymerizable composition is a composition containing a monomer mixture containing a polymerizable monomer or a partial polymer thereof as an essential component.
- a polymerizable composition is apply
- the “monomer mixture” means a mixture composed only of monomer components, and includes a case composed of only one monomer component.
- the “partially polymerized product” means a composition in which one or more components of the monomer mixture are partially polymerized.
- the polymerizable monomer is a compound that can be polymerized using light energy or heat energy regardless of the reaction mechanism such as radical polymerization or cationic polymerization.
- the polymerizable monomer at least one kind that can interact with the polymer sheet as the monomer absorption layer, is absorbed by the polymer sheet, and can move to the inside of the layer is selected. It is important to use them.
- polymerizable monomers examples include radical polymerizable monomers such as acrylic monomers that form acrylic polymers; epoxy monomers that form epoxy resins, oxetane monomers that form oxetane resins, and vinyl ether resins.
- a cationically polymerizable monomer such as a vinyl ether monomer that forms a resin; a combination of a polyisocyanate that forms a urethane resin and a polyol; a combination of a polycarboxylic acid that forms a polyester resin, a polyol, and the like.
- a polymerizable monomer can be used individually or in combination of 2 or more types.
- the polymerizable composition is a polymerizable acrylic composition (acrylic polymerizable) having a monomer mixture containing an acrylic monomer as a main component or a partial polymer thereof (acrylic monomer mixture or a partial polymer thereof) as an essential component. It is preferable that it is a composition).
- acrylic monomer examples include (meth) acrylic acid esters, in particular, (meth) acrylic acid alkyl esters having an alkyl group ((meth) acrylic acid alkyl esters having a linear or branched alkyl group, cyclic alkyl groups). (Meth) acrylic acid alkyl ester) having In addition, said “(meth) acryl” represents “acryl” and / or "methacryl", and others are the same. In addition, (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.
- Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.
- (meth) acrylic acid alkyl esters having 1 to 14 carbon atoms in the alkyl group are preferable, and (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms in the alkyl group are more preferable.
- Examples of the (meth) acrylic acid alkyl ester having a cyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
- (meth) acrylic acid ester When the polymerizable composition is a polymerizable acrylic composition, (meth) acrylic acid ester [particularly, (meth) acrylic acid having an alkyl group (for example, a linear or branched alkyl group or a cyclic alkyl group) It is important that the alkyl ester] occupies 60% by weight or more (preferably 90% by weight or more) of the total monomer components of the acrylic monomer mixture or its partial polymer.
- polymerizable acrylic composition as a forming component of the acrylic monomer mixture or a partial polymer thereof, in addition to the acrylic monomer as the main forming component, various copolymers such as polar group-containing monomers and polyfunctional monomers May be used.
- a copolymerizable monomer is advantageous in that, for example, the cohesive force can be increased.
- a copolymerizable monomer can be used individually or in combination of 2 or more types.
- Examples of the polar group-containing monomer include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid or anhydrides thereof (such as maleic anhydride); Hydroxyl-containing monomers such as hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N, N-dimethyl (meth) acrylamide, Amide group-containing monomers such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Meta Amino group-containing monomers such as t-butylaminoeth
- the use amount of the polar group-containing monomer is 30% by weight or less (for example, 1 to 30% by weight), preferably 3 to 20%, based on the total amount of the monomer components as a component for forming the acrylic monomer mixture or its partial polymer. % By weight.
- the usage-amount of a polar group containing monomer exceeds 30 weight%, cohesion force will become high too much, for example, a malfunction may be produced in the point of a softness
- there is too little usage-amount of a polar group containing monomer for example, it is less than 1 weight% with respect to the monomer component whole quantity for forming an acrylic polymer), the cohesion force of the polymer obtained will fall and high intensity
- polyfunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl.
- the amount of the polyfunctional monomer used is not particularly limited and can be used within the range not impairing the effects of the present invention.
- copolymerizable monomers other than polar group-containing monomers and polyfunctional monomers examples include vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; ethylene, butadiene, and isoprene. And olefins or dienes such as isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride and the like.
- Examples of the copolymerizable monomer other than the polar group-containing monomer include (meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate; (meth) acrylic acid other than the polar group-containing monomer Esters; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyl compounds such as styrene and vinyl toluene; Olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; Vinyl ethers such as vinyl alkyl ether; Vinyl chloride and the like Is mentioned.
- the polymerizable composition is preferably a photopolymerizable composition, and particularly preferably a photopolymerizable acrylic composition.
- At least one of the polymerizable composition and the polymer sheet starts photopolymerization because the polymerizable monomer in the polymerizable composition is absorbed by the polymer sheet as the monomer absorption layer. It only has to contain an agent. Moreover, in the polymer sheet as a monomer absorption layer, it forms with the monomer absorption layer formation composition containing a photoinitiator, As a result, the photoinitiator may be contained in this polymer sheet.
- the photopolymerization initiator is not particularly limited.
- benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime.
- a photopolymerization initiator, a benzoin photopolymerization initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, or the like can be used.
- a photoinitiator can be used individually or in combination of 2 or more types.
- the ketal photopolymerization initiator includes, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one [for example, trade name “Irgacure 651” (manufactured by Ciba Japan)] Etc. are included.
- examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [for example, trade name “Irgacure 184” (manufactured by Ciba Japan)], 2,2-diethoxyacetophenone, 2,2-dimethoxy- Examples include 2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
- acylphosphine oxide photopolymerization initiator for example, trade name “Lucirin TPO” (manufactured by BASF) can be used.
- ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. .
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
- Examples of the benzoin photopolymerization initiator include benzoin.
- Examples of the benzyl photopolymerization initiator include benzyl.
- benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
- the amount of the photopolymerization initiator used is not particularly limited.
- the polymerizable composition is a photopolymerizable acrylic composition
- 100 parts by weight of an acrylic monomer mixture which is an essential component or a partial polymer thereof. can be selected from the range of 0.01 to 5 parts by weight (preferably 0.05 to 3 parts by weight).
- Examples of the active energy rays irradiated during the curing reaction using the active energy rays include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, and electron beams, and ultraviolet rays, and particularly ultraviolet rays. Is preferred.
- the irradiation energy, irradiation time, irradiation method, and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause a polymerization reaction.
- thermal polymerization initiator examples include azo polymerization initiators [for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′- Azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'- Dimethyleneisobutylamidine) dihydrochloride, etc.], peroxide-based polymerization initiators (for example, dibenzoyl peroxide, tert-butylpermaleate).
- azo polymerization initiators for example, 2,2′-azobisisobutyronitrile
- Redox polymerization initiators such as organic peroxide / vanadium compound; the organic peroxide / dimethylaniline; naphthenic acid metal salt / butyl aldehyde, a combination such as aniline or acetylbutyrolactone, and the like.
- the amount of the thermal polymerization initiator used is not particularly limited as long as it can be used as a thermal polymerization initiator. If a redox polymerization initiator is used as a thermal polymerization initiator, it can be polymerized at room temperature.
- a crosslinker may be added to the polymerizable composition.
- the crosslinking agent an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, A carbodiimide type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, an amine type crosslinking agent, etc. are mentioned.
- a crosslinking agent can be used individually or in combination of 2 or more types.
- isocyanate-based crosslinking agent examples include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone.
- Alicyclic polyisocyanates such as diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.
- Aromatic polyisocyanates and the like, and other trimethylolpropane / tolylene diisocyanate adduct [manufactured by Nippon Polyurethane Industry Co., Ltd., Name "Coronate L”], trimethylolpropane / hexamethylene diisocyanate adduct [Nippon Polyurethane Industry Co., Ltd. under the trade name "Coronate HL”], and the like are also used.
- epoxy-based crosslinking agent examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1 , 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyg In addition to sidyl ether, a
- the amount of the crosslinking agent used is not particularly limited.
- the polymerizable composition is a photopolymerizable acrylic composition, from the viewpoint of preventing the polymerization by coloring or brittleness after curing, or light absorption.
- the amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the acrylic monomer mixture which is an essential component or a partial polymer thereof.
- the polymerizable composition may contain an appropriate additive as necessary.
- additives include surfactants (for example, ionic surfactants, silicone surfactants, fluorosurfactants, etc.), tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum Resin, oil-soluble phenol resin, etc., which are solid, semi-solid or liquid at normal temperature), plasticizers, fillers, anti-aging agents, antioxidants, colorants (pigments, dyes, etc.).
- the amount of these additives can be appropriately selected within a range not impairing the effects of the present invention.
- the polymerizable composition may contain at least one “substance that is not absorbed by the polymer sheet (polymer sheet as the monomer absorption layer)” as a forming component.
- a substance that is not absorbed by the polymer sheet can be determined by dissolving or not dissolving the monomer that forms the polymer sheet as the monomer absorption layer. Specifically, whether or not a certain substance falls under “substance not absorbed by the polymer sheet” depends on the monomer that forms the polymer sheet and the certain substance (if there are multiple monomers to be formed, a mixture of monomers that forms) It is judged by mixing at a ratio of 1: 1 (weight ratio). For example, when it does not dissolve at all in the monomer forming the polymer sheet, it is “a substance that is not absorbed by the polymer sheet”.
- the cloudy state refers to a state that is visually determined to be cloudy rather than transparent.
- a polymer compound having a molecular weight of 100,000 or more is a substance that is not absorbed by the polymer sheet.
- the “substance that is not absorbed by the polymer sheet (polymer sheet as the monomer absorption layer)” is not particularly limited, and may be an organic substance or an inorganic substance. Moreover, it may be a solid material and may have fluidity. Furthermore, it can be used alone or in combination of two or more.
- the polymerizable composition contains a substance that is not absorbed by the polymer sheet as the monomer absorption layer as a forming component, the surface of the polymer sheet having a three-dimensional pattern, for example, hardness, flexibility, adhesion It is possible to impart properties and optical characteristics.
- Such materials are not particularly limited, but silica, silicone (silicone powder), calcium carbonate, clay, titanium oxide, talc, layered silicate, clay mineral, metal powder, glass, glass beads, glass balloon, alumina
- Inorganic particles such as balloon, ceramic balloon, titanium white, carbon black, activated carbon, barium titanate; organic particles such as polyester beads, nylon beads, silicon beads, urethane beads, vinylidene chloride beads, acrylic balloons; crosslinked acrylic particles, crosslinked styrene Particles such as particles, resin particles such as melamine resin particles, benzoguanamine resin and nylon resin; particles such as inorganic-organic hybrid particles are preferable.
- the particles may be solid or hollow (balloon).
- the particle size (average particle size) of the particles is not particularly limited, but can be selected from the range of 0.5 to 500 ⁇ m (preferably 1 to 300 ⁇ m, more preferably 3 to 100 ⁇ m), for example.
- the shape of the particles is not particularly limited, and may be any shape such as a spherical shape such as a true spherical shape or an elliptic spherical shape, an indefinite shape, a needle shape, a rod shape, or a flat plate shape.
- the particles may have holes or protrusions on the surface.
- Various surface treatments for example, a low surface tension treatment with a silicone compound, a fluorine compound, or the like) may be applied to the surface of the particles.
- the substance that is not absorbed by the polymer sheet as the monomer absorption layer include acrylic polymers, polyesters, polyurethanes, polyethers, silicones, natural rubbers, synthetic rubbers [in particular, styrene-isoprene-styrene rubber (SIS), Synthetic rubber containing styrene component such as styrene-butadiene-styrene rubber (SBS) or styrene-ethylene-butylene-styrene rubber (SEBS) and oligomers thereof; rosin-based tackifier resin, terpene-based tackifier resin , Phenolic tackifier resins, hydrocarbon tackifier resins, ketone tackifier resins, polyamide tackifier resins, epoxy tackifier resins, elastomer tackifier resins, etc.
- SIS styrene-isoprene-styrene rubber
- SBS s
- tackifiers tackifier resins
- surface activity Agent antioxidant, Pigments, plasticizers, solvents (organic solvent) and the like liquids such as.
- solvents organic solvent
- water and aqueous solution for example, salt aqueous solution, acid aqueous solution, etc. are also mentioned.
- the property inherent to the substance in the three-dimensional pattern of the polymer sheet having a three-dimensional pattern on the surface for example, using rubber
- Flexibility when used tackiness when using a tackifying resin, colorability when using a pigment, water content when using water or an aqueous solution, etc.
- the above-mentioned particles, SEBS, polyester, silicone, etc. can be preferably used as the substance that is not absorbed by the polymer sheet. .
- an acrylic polymer is used as a polymer for forming a polymer sheet as a monomer absorption layer and particles are used as a substance that is not absorbed in the polymer sheet, in the polymer sheet having a three-dimensional pattern on the surface obtained by the production method of the present invention, This produces an effect of concentrating particles near the surface on which the three-dimensional pattern is formed.
- cross-linked acrylic particles, layered silicate, silica, barium titanate, titanium oxide, or the like is used as particles, it is possible to easily impart surface functions such as increasing the surface hardness.
- the amount used in the case where the polymerizable composition contains a substance that is not absorbed by the polymer sheet is not particularly limited, but for example, when the polymerizable composition is a photopolymerizable acrylic composition,
- the amount is preferably 0.01 to 50 parts by weight, and preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of a certain acrylic monomer mixture or a partial polymer thereof.
- the amount exceeds 50 parts by weight, it may be difficult to produce a polymer sheet having a three-dimensional pattern on the surface or a problem of strength may occur.
- the amount is less than 0.01 parts by weight, the substance is added. The effect may not be obtained.
- the polymerizable composition is the above-described monomer-absorbing layer-forming composition from the viewpoint of ease of forming a three-dimensional surface pattern and ease of work due to the ease of migration of the polymerizable monomer. It is preferable to have the same or similar composition.
- a polymerizable composition having at least one main monomer component forming the monomer absorption layer forming composition as a polymerizable monomer, and a monomer of the main monomer component forming the monomer absorption layer forming composition examples thereof include a polymerizable composition having a monomer having a common partial structure (for example, an acrylate structure portion of an acrylic monomer, an epoxy structure portion of an epoxy monomer) as a polymerizable monomer.
- an acrylic polymer when used as the polymer constituting the polymer sheet as the monomer absorption layer, it is preferable to use an acrylic monomer as the polymerizable monomer of the polymerizable composition.
- the polymerizable composition can be prepared by mixing and dispersing the above components uniformly. Since this polymerizable composition is usually formed into a sheet by coating on a polymer sheet as a monomer absorption layer, it is preferable to have an appropriate viscosity suitable for the coating operation.
- the viscosity of the polymerizable composition can be adjusted by, for example, blending various polymers such as acrylic rubber and a thickening additive, or by partially polymerizing by irradiation with light or heating.
- a desirable viscosity is a rotor: No. The viscosity set under the conditions of 5 rotors, 10 rpm, and measurement temperature: 30 ° C.
- the viscosity is 5 to 50 Pa ⁇ s, more preferably 10 to 40 Pa ⁇ s. If the viscosity is less than 5 Pa ⁇ s, the liquid flows when applied, and if it exceeds 50 Pa ⁇ s, the viscosity is too high to make application difficult.
- the polymer sheet having a three-dimensional pattern on the surface is coated with the polymerizable composition on one side of the polymer sheet as the monomer absorption layer, and the surface shape of the surface on which the polymerizable composition is applied is formed. It is formed through a step of changing three-dimensionally [step (i)] and a step of forming a three-dimensional pattern on the surface [step (ii)].
- step (i) the polymerizable composition is applied on one side of the polymer sheet as the monomer absorption layer, that is, on the monomer absorption surface of the polymer sheet.
- the polymerizable composition is applied, a change from a smooth shape to a three-dimensional solid shape occurs on the surface of the polymer sheet on which the polymerizable composition is applied. That is, on the surface on which the polymerizable composition is applied, a three-dimensional pattern is formed over time although it is smooth immediately after being applied.
- the manufacturing method of this invention after forming this 3D-shaped pattern, it is attached
- step (i) by applying the polymerizable composition to the polymer sheet as the monomer absorption layer, an interaction occurs between the polymer sheet and at least one of the polymerizable monomers, and the interaction occurs. It is estimated that the polymerizable monomer is at least partially absorbed into the interior of the polymer sheet, and the volume change or movement (shape change) of the applied polymerizable composition occurs as the volume of the polymer sheet increases (swells).
- step (i) the structure obtained by applying the polymerizable composition to the polymer sheet as the monomer absorption layer is obtained by changing the surface shape of the surface on which the polymerizable composition is applied. Leave until a three-dimensional structure is obtained.
- the environment where the polymerization is allowed to proceed is usually cured as the polymerization proceeds, and a desired three-dimensional structure may not be obtained. Therefore, it is preferable that the polymerization reaction does not proceed so much or an environment where no polymerization reaction occurs at all.
- the standing time (time from application of the polymerizable composition on the polymer sheet to polymerization) is not particularly limited, but productivity and formation of a three-dimensional structure are not particularly limited. From the point, 1 minute or more is preferable, preferably 2 minutes or more, and more preferably 3 minutes or more. In addition, the time of process (ii) is usually within 1 hour (preferably within 30 minutes). It is because volatilization of the polymerizable composition occurs if left too long.
- step (i) usually a cover film is not used.
- a polymerizable composition comprising, as an essential component, a monomer mixture containing at least one polymerizable monomer that can be absorbed by the polymer sheet or a partial polymer thereof on one side of the polymer sheet.
- step (ii) the structure obtained in step (i) (the structure obtained by applying the polymerizable composition to the polymer sheet as the monomer absorption layer was allowed to stand and the polymerizable composition was applied.
- a polymer sheet having a desired three-dimensional structure on the side surface is subjected to polymerization and cured to form a three-dimensional pattern (three-dimensional pattern) of a polymer sheet having a three-dimensional pattern on the surface.
- Examples of the polymerization include thermal polymerization when a polymerizable composition containing a thermal polymerization initiator is used, and photopolymerization when a polymerizable composition containing a photopolymerization initiator is used. As described above, it is preferable to use a photopolymerization method from the viewpoint of easy availability of a thick polymer sheet, workability, and not requiring a large amount of energy for heating and cooling.
- a light source or heat source irradiation energy or thermal energy
- irradiation method or heating method irradiation time or heating time
- irradiation or heating start time There are no particular restrictions on the end of irradiation or heating.
- Examples of the active energy rays irradiated in the photopolymerization include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, and electron rays, and ultraviolet rays. Is preferred.
- examples of the method for polymerization by photopolymerization by ultraviolet irradiation include ultraviolet irradiation by a black light lamp, a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.
- the well-known heating method for example, the heating method using an electric heater, the heating method using electromagnetic waves, such as infrared rays, etc. is mentioned, for example.
- Such a method for producing a polymer sheet having a three-dimensional pattern on the surface is simple, and can produce a polymer sheet having a three-dimensional pattern on the surface with good workability. Further, the surface area can be increased. Furthermore, when the photopolymerization method is employed, it is not necessary to provide a heating step for promoting polymerization, a cooling step for suppressing runaway reaction, and the like, and the energy saving property is excellent.
- the polymer sheet having a three-dimensional pattern on the surface produced by the production method of the present invention has a three-dimensional pattern on at least one surface. For this reason, it is excellent in design property. Furthermore, the surface area is large.
- the three-dimensional pattern of the polymer sheet having a three-dimensional pattern on the surface is an unspecified shape, for example, a pleated peak (a pleated object, a saddle-like object, a saddle-shaped ridge) and a concave valley (an indented part). ), And has a shape such as an irregular three-dimensional network in which the pleated ridges irregularly intersect each other, and a melon net shape on the surface of a plant mask melon (see FIGS. 2 to 6, 10, and 11).
- the height of the peak portion in the polymer sheet having a three-dimensional pattern on the surface is not particularly limited, but is, for example, about 10 to 2000 ⁇ m, and preferably about 100 to 500 ⁇ m.
- the height is represented by the difference between the deepest part of the valley and the highest part of the mountain.
- the thickness of the entire polymer sheet having a three-dimensional pattern on the surface is not particularly limited, but is, for example, about 50 to 3000 ⁇ m, and preferably about 200 to 1000 ⁇ m.
- the total thickness corresponds to the thickness of the polymer portion obtained by subjecting the structure formed from the polymer sheet as the monomer absorption layer and the polymerizable composition to polymerization, and has a three-dimensional surface. It is the thickness of the thickest part in the entire polymer sheet having a pattern.
- the thickness of the entire polymer sheet having a three-dimensional pattern on the surface does not include the thickness of the support.
- Such a polymer sheet having a three-dimensional pattern on the surface can be used, for example, for design such as design utilizing the surface shape, anti-slip, or for use such as adsorption, absorption or release of substances utilizing the surface area. It can be used for table cloths, flooring materials, ceiling materials, wallpaper, interior materials for automobiles, exterior materials for portable electronic devices such as mobile phones.
- a monomer component As a monomer component, a monomer mixture in which 2-ethylhexyl acrylate: 90 parts by weight and acrylic acid: 10 parts by weight are mixed, and a photopolymerization initiator (trade name “Irgacure 651” manufactured by Ciba Japan): 0.1 weight was stirred until it became uniform in a four-necked separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and cooling tube, and dissolved oxygen was removed by bubbling with nitrogen gas for 1 hour. . Thereafter, the composition was polymerized by irradiating ultraviolet light from the outside of the flask with a black light lamp.
- a photopolymerization initiator trade name “Irgacure 651” manufactured by Ciba Japan
- a photopolymerizable composition (sometimes referred to as “photopolymerizable composition (A)”) was prepared.
- a photopolymerizable composition (sometimes referred to as “photopolymerizable composition (D)”) was prepared.
- the cover film has a biaxially stretched polyethylene terephthalate film (trade name “MRN38” manufactured by Mitsubishi Plastics, Inc., or “MRF38” Mitsubishi Plastics) having a thickness of 38 ⁇ m, one side of which has been release-treated with a silicone-based release agent (release agent). Used).
- MRN38 polyethylene terephthalate film
- MRF38 silicone-based release agent
- the photopolymerizable composition (A) is applied to one side of a PET base material (biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.) so that the thickness after curing is 30 ⁇ m.
- the coating layer was applied to form a coating layer, and the cover film was bonded to the layer so that the release-treated surface was in contact therewith.
- ultraviolet rays (illuminance: 5 mW / cm 2 ) were irradiated for 3 minutes using a black light, and the layer was cured to obtain a polymer sheet. Thereafter, the cover film was peeled off and removed to prepare a polymer sheet provided on the PET substrate (sometimes referred to as “polymer sheet with PET substrate (A)”).
- the photopolymerizable composition (D) is applied to one side of a PET substrate (biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.) so that the thickness after curing is 30 ⁇ m.
- the coating layer was applied to form a coating layer, and the cover film was bonded to the layer so that the release-treated surface was in contact therewith.
- ultraviolet rays (illuminance: 5 mW / cm 2 ) were irradiated for 3 minutes using a black light, and the layer was cured to obtain a polymer sheet. Thereafter, the cover film was peeled off and removed to prepare a polymer sheet provided on the PET substrate (sometimes referred to as “polymer sheet with PET substrate (B)”).
- PET base material biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.
- a coating layer was formed, and a cover film was bonded to the layer so that the surface subjected to the release treatment was in contact with the layer.
- ultraviolet rays (illuminance: 5 mW / cm 2 ) were irradiated for 3 minutes using a black light, and the layer was cured to obtain a polymer sheet.
- the polymer sheet provided on the PET base material may be referred to as “polymer sheet with PET base material (C)” was prepared by peeling off and removing the cover film.
- the photopolymerizable composition (A) is applied to one side of a PET base material (biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.) so that the thickness after curing becomes 100 ⁇ m.
- the coating layer was applied to form a coating layer, and the cover film was bonded to the layer so that the release-treated surface was in contact therewith.
- ultraviolet rays (illuminance: 5 mW / cm 2 ) were irradiated for 3 minutes using a black light, and the layer was cured to obtain a polymer sheet. Thereafter, the cover film was peeled off and removed to prepare a polymer sheet provided on the PET substrate (sometimes referred to as “polymer sheet with PET substrate (D)”).
- the photopolymerizable composition (A) is applied to one side of a PET base material (biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.) so that the thickness after curing is 200 ⁇ m.
- the coating layer was applied to form a coating layer, and the cover film was bonded to the layer so that the release-treated surface was in contact therewith.
- ultraviolet rays (illuminance: 5 mW / cm 2 ) were irradiated for 3 minutes using a black light, and the layer was cured to obtain a polymer sheet.
- the cover film was peeled off and removed to prepare a polymer sheet (sometimes referred to as “polymer sheet with PET substrate (E)”) provided on the PET substrate.
- Example 1 On the polymer sheet of the polymer sheet (A) with a PET substrate, the photopolymerizable composition (B) was applied so as to have a thickness of 100 ⁇ m. When allowed to stand for 10 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass through UV irradiation apparatus with a conveyor 5 times with the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2
- the light intensity per time was 830 mJ / cm 2 .
- a monomer solution (2-ethylhexyl acrylate: 90 parts by weight and acrylic acid: 10 parts by weight
- Example 2 On the polymer sheet of the polymer sheet (A) with a PET substrate, the photopolymerizable composition (B) was applied so as to have a thickness of 200 ⁇ m. When allowed to stand for 5 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass through UV irradiation apparatus with a conveyor 5 times with the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2
- the light intensity per time was 830 mJ / cm 2 .
- Example 3 On the polymer sheet of the polymer sheet (A) with a PET substrate, the photopolymerizable composition (B) was applied so as to have a thickness of 400 ⁇ m. When left for 3 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass 5 times to UV irradiation apparatus with a conveyor at the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2 and the light intensity per time was 830 mJ / cm 2 .
- Example 4 On the polymer sheet of the polymer sheet (B) with a PET substrate, the photopolymerizable composition (C) was applied so as to have a thickness of 100 ⁇ m. When allowed to stand for 10 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass through UV irradiation apparatus with a conveyor 5 times with the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2
- the light intensity per time was 830 mJ / cm 2 .
- the polymer sheet taken out from the polymer sheet (B) with the PET base material was immersed in an excess amount of the monomer solution (butyl acrylate: 10 parts by weight) having the same composition as the photopolymerizable composition (C) at 25 ° C. Sometimes the polymer sheet gained 5.7 times the initial weight after 75 seconds and 11.2 times the initial weight after 3 days.
- Example 5 On the polymer sheet of the polymer sheet (A) with a PET substrate, the photopolymerizable composition (E) was applied so as to have a thickness of 100 ⁇ m. When allowed to stand for 10 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass through UV irradiation apparatus with a conveyor 5 times with the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2
- the light intensity per time was 830 mJ / cm 2 .
- the crosslinked polymer particles having an average particle diameter of 5 ⁇ m contained in the photopolymerizable composition (E) are substances that are not absorbed by the polymer sheet.
- Example 6 The photopolymerizable composition (B) was applied on the polymer sheet of the polymer sheet (A) with a PET substrate so as to have a thickness of 100 ⁇ m. When allowed to stand for 10 minutes after application, a three-dimensional pattern was formed on the surface of the application surface. Next, UV irradiation was performed using a UV irradiation apparatus with a conveyor (with a fusion H bulb as a UV lamp) with the coated surface facing up. The three-dimensional pattern was fixed by the ultraviolet irradiation to obtain a polymer sheet having the three-dimensional pattern formed on the sheet surface.
- UV irradiation was performed by making it pass through UV irradiation apparatus with a conveyor 5 times with the conveyor speed of 3.5 m / min.
- the UV illuminance per time was 290 mW / cm 2
- the light intensity per time was 830 mJ / cm 2 .
- the photopolymerizable composition (B) is formed on one surface of a PET substrate (biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.). Was applied to a thickness of 100 ⁇ m. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface. In addition, when the PET substrate was immersed at 25 ° C.
- PET The substrate gained 1.1 times its initial weight after 75 seconds and 1.1 times its initial weight after 3 days.
- the photopolymerizable composition (B) is formed on one surface of a PET substrate (biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.). Was applied to a thickness of 200 ⁇ m. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface.
- a PET substrate biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.
- the photopolymerizable composition (B) is formed on one surface of a PET substrate (biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.). Was applied so as to be 400 ⁇ m. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface.
- a PET substrate biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.
- the photopolymerizable composition (C) is formed on one surface of a PET substrate (biaxially stretched polyethylene terephthalate film having a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.). Was applied to a thickness of 100 ⁇ m. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface.
- a PET base material was immersed in an excess amount of a monomer solution (butyl acrylate: 100 parts by weight) having the same composition as the photopolymerizable composition (C) at 25 ° C.
- the PET base material had an initial weight after 75 seconds. The weight increased to 1.1 times the initial weight after 1.1 days.
- the photopolymerizable composition (E) is formed on one surface of a PET substrate (biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.). Was applied to a thickness of 100 ⁇ m. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface.
- a PET substrate biaxially stretched polyethylene terephthalate film with a thickness of 38 ⁇ m, trade name “Lumirror S10” manufactured by Toray Industries, Inc.
- the photopolymerizable composition (B) was applied to a thickness of 200 ⁇ m on the polymer sheet of the polymer sheet (C) with a PET substrate. Even after 1 hour from application, a three-dimensional pattern was not formed on the surface of the application surface. In addition, it took out from the polymer sheet (C) with a PET base material in an excessive amount of a monomer solution (2-ethylhexyl acrylate: 90 parts by weight and acrylic acid: 10 parts by weight) having the same composition as the photopolymerizable composition (B). When the polymer sheet was immersed at 25 ° C., the polymer sheet increased in weight to 3.8 times the initial weight after 75 seconds, but almost dissolved after 3 days and decreased to 0.03 times the initial weight. .
- one scale of the scale is 50 ⁇ m.
- one scale of the scale is 100 ⁇ m.
- one scale of the scale is 100 ⁇ m.
- one scale of the scale is 100 ⁇ m.
- one scale of the scale is 100 ⁇ m.
- one scale of the scale is 100 ⁇ m.
- one scale scale is 10 ⁇ m.
- one scale of the scale is 50 ⁇ m.
- one scale scale is 10 ⁇ m.
- one scale of the scale is 0.5 mm.
- one scale of the scale is 100 ⁇ m.
- one scale of the scale is 50 ⁇ m.
- the polymer sheet having a three-dimensional pattern on the surface is used, for example, for design such as design utilizing the surface shape, anti-slip, or for use such as adsorption, absorption or release of a substance utilizing the surface area. It is also used for table cloths, flooring materials, ceiling materials, wallpaper, automobile interior materials, exterior materials for portable electronic devices such as mobile phones.
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Abstract
Description
ポリマーシートは、単層のポリマー層からなるシートであり、重合性組成物の重合性モノマーのうち少なくとも一種を重合性組成物から吸収することができる。つまり、本願にいう「ポリマーシート」は、モノマー吸収層として作用するシート形状あるいはフィルム形状のポリマーのことをいう。前記のモノマー吸収層とは、重合性モノマーのうち少なくとも一種との間で相互作用を生じ、該重合性モノマーを吸い、層内部まで移動させることが可能な層(層内部に取り込むことが可能な層)のことをいう。また、ポリマーシートにおいて、モノマー吸収層により提供される面は、重合性モノマーを吸収する面、すなわちモノマー吸収面である。
重合性組成物は、重合性モノマーを含むモノマー混合物又はその部分重合物を必須成分とする組成物である。重合性組成物は、前記のモノマー吸収層としてのポリマーシート上に塗布される。なお、「モノマー混合物」はモノマー成分のみからなる混合物を意味し、また1つのモノマー成分のみからなる場合を含むものとする。また、「部分重合物」はモノマー混合物のうち1つ又は2つ以上の成分が部分的に重合している組成物を意味する。
本発明によれば、表面に3次元模様を有するポリマーシートは、モノマー吸収層としてのポリマーシートの片面に、重合性組成物を塗布し、重合性組成物を塗布した側の面の表面形状を3次元的に変化させる工程[工程(i)]、重合に付して、表面に3次元模様を形成する工程[工程(ii)]を経て形成される。
本発明の製造方法により作製された表面に3次元模様を有するポリマーシートは、少なくとも一方の表面に、3次元模様を有する。このため、意匠性に優れている。さらに、表面積が大きい。
モノマー成分として、2−エチルヘキシルアクリレート:90重量部、およびアクリル酸:10重量部が混合されたモノマー混合物と、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):0.1重量部とを、攪拌機、温度計、窒素ガス導入管、冷却管を備えた4つ口のセパラブルフラスコ中で均一になるまで攪拌した後、窒素ガスによりバブリングを1時間行って溶存酸素を除去した。その後、ブラックライトランプにより紫外線をフラスコ外側より照射して重合し、適度な粘度になった時点でランプを消灯、窒素吹き込みを停止して、重合率7%の一部が重合した組成物(シロップ)(「光重合性シロップ(A)」と称する場合がある)を調製した。
モノマー成分としてのブチルアクリレート:100重量部と、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):0.1重量部とを、攪拌機、温度計、窒素ガス導入管、冷却管を備えた4つ口のセパラブルフラスコ中で均一になるまで攪拌した後、窒素ガスによりバブリングを1時間行って溶存酸素を除去した。その後、ブラックライトランプにより紫外線をフラスコ外側より照射して重合し、適度な粘度になった時点でランプを消灯、窒素吹き込みを停止して、重合率7%の一部が重合した組成物(シロップ)(「光重合性シロップ(B)」と称する場合がある)を調製した。
モノマー成分としてのイソボルニルアクリレート:100重量部と、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):0.1重量部とを、攪拌機、温度計、窒素ガス導入管、冷却管を備えた4つ口のセパラブルフラスコ中で均一になるまで攪拌した後、窒素ガスによりバブリングを1時間行って溶存酸素を除去した。その後、ブラックライトランプにより紫外線をフラスコ外側より照射して重合し、適度な粘度になった時点でランプを消灯、窒素吹き込みを停止して、重合率7%の一部が重合した組成物(シロップ)(「光重合性シロップ(C)」と称する場合がある)を調製した。
光重合性シロップ(A):100重量部に、架橋剤として1,6−ヘキサンジオールジアクリレート(商品名「NKエステルA−HD」新中村化学社製):0.1重量部を混合して、光重合性組成物(「光重合性組成物(A)」と称する場合がある)を調製した。
光重合性シロップ(A):100重量部に、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):2重量部、架橋剤としてジペンタエリスリトールヘキサアクリレート(商品名「カヤラッドDPHA」日本化薬社製):0.3重量部を溶解・混合して、光重合性組成物(「光重合性組成物(B)」と称する場合がある)を調製した。
光重合性シロップ(B):100重量部に、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):2重量部、架橋剤としてジペンタエリスリトールヘキサアクリレート(商品名「カヤラッドDPHA」日本化薬社製):0.3重量部を溶解・混合して、光重合性組成物(「光重合性組成物(C)」と称する場合がある)を調製した。
光重合性シロップ(C):100重量部に、架橋剤として1,6−ヘキサンジオールジアクリレート(商品名「NKエステルA−HD」新中村化学社製):0.1重量部を混合して、光重合性組成物(「光重合性組成物(D)」と称する場合がある)を調製した。
光重合性シロップ(A):100重量部に、光重合開始剤(商品名「イルガキュア651」チバ・ジャパン社製):2重量部、架橋剤としてジペンタエリスリトールヘキサアクリレート(商品名「カヤラッドDPHA」日本化薬社製):0.3重量部、平均粒径5μmの架橋ポリマー粒子(商品名「MX−500」綜研化学社製):5重量部を混合して、光重合性組成物(「光重合性組成物(E)」と称する場合がある)を調製した。
カバーフィルムは、片面がシリコーン系離型処理剤(剥離剤)により離型処理された、厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム(商品名「MRN38」三菱樹脂社製、あるいは「MRF38」三菱樹脂社製)を用いた。
光重合性組成物(A)を、PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の片面に、硬化後の厚さが30μmとなるように塗布し塗布層を形成して、該層上に離型処理された面が接する形態でカバーフィルムを貼り合わせた。次に、ブラックライトを用いて紫外線(照度:5mW/cm2)を3分間照射し、該層を硬化させ、ポリマーシートを得た。その後、カバーフィルムを剥がして除去することにより、PET基材上に設けられたポリマーシート(「PET基材付きポリマーシート(A)」と称する場合がある)を作製した。
光重合性組成物(D)を、PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の片面に、硬化後の厚さが30μmとなるように塗布し塗布層を形成して、該層上に離型処理された面が接する形態でカバーフィルムを貼り合わせた。次に、ブラックライトを用いて紫外線(照度:5mW/cm2)を3分間照射し、該層を硬化させ、ポリマーシートを得た。その後、カバーフィルムを剥がして除去することにより、PET基材上に設けられたポリマーシート(「PET基材付きポリマーシート(B)」と称する場合がある)を作製した。
光重合性シロップ(A)を、PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の片面に、硬化後の厚さが50μmとなるように塗布し塗布層を形成して、該層上に離型処理された面が接する形態でカバーフィルムを貼り合わせた。次に、ブラックライトを用いて紫外線(照度:5mW/cm2)を3分間照射し、該層を硬化させ、ポリマーシートを得た。その後、カバーフィルムを剥がして除去することにより、PET基材上に設けられたポリマーシート(「PET基材付きポリマーシート(C)」と称する場合がある)を作製した。
光重合性組成物(A)を、PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の片面に、硬化後の厚さが100μmとなるように塗布し塗布層を形成して、該層上に離型処理された面が接する形態でカバーフィルムを貼り合わせた。次に、ブラックライトを用いて紫外線(照度:5mW/cm2)を3分間照射し、該層を硬化させ、ポリマーシートを得た。その後、カバーフィルムを剥がして除去することにより、PET基材上に設けられたポリマーシート(「PET基材付きポリマーシート(D)」と称する場合がある)を作製した。
光重合性組成物(A)を、PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の片面に、硬化後の厚さが200μmとなるように塗布し塗布層を形成して、該層上に離型処理された面が接する形態でカバーフィルムを貼り合わせた。次に、ブラックライトを用いて紫外線(照度:5mW/cm2)を3分間照射し、該層を硬化させ、ポリマーシートを得た。その後、カバーフィルムを剥がして除去することにより、PET基材上に設けられたポリマーシート(「PET基材付きポリマーシート(E)」と称する場合がある)を作製した。
PET基材付きポリマーシート(A)のポリマーシート上に、光重合性組成物(B)を、厚さが100μmとなるように塗布した。塗布から10分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
なお、光重合性組成物(B)と同じ組成のモノマー溶液(2−エチルヘキシルアクリレート:90重量部とアクリル酸:10重量部)の過剰量に、PET基材付きポリマーシート(A)から取り出したポリマーシートを25℃で浸漬したとき、該ポリマーシートは、75秒後に初期重量の4.2倍、3日後に初期重量の12.6倍に重量増加した。
PET基材付きポリマーシート(A)のポリマーシート上に、光重合性組成物(B)を厚さが200μmとなるように塗布した。塗布から5分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
PET基材付きポリマーシート(A)のポリマーシート上に、光重合性組成物(B)を厚さが400μmとなるように塗布した。塗布から3分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
PET基材付きポリマーシート(B)のポリマーシート上に、光重合性組成物(C)を厚さが100μmとなるように塗布した。塗布から10分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
なお、光重合性組成物(C)と同じ組成のモノマー溶液(アクリル酸ブチル:10重量部)の過剰量に、PET基材付きポリマーシート(B)から取り出したポリマーシートを25℃で浸漬したとき、該ポリマーシートは75秒後に初期重量の5.7倍、3日後に初期重量の11.2倍に重量増加した。
PET基材付きポリマーシート(A)のポリマーシート上に、光重合性組成物(E)を厚さが100μmとなるように塗布した。塗布から10分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
また、光重合性組成物(E)に含まれる平均粒径5μmの架橋ポリマー粒子は、ポリマーシートに吸収されない物質である。
PET基材付きポリマーシート(A)のポリマーシート上に、光重合性組成物(B)を厚さが100μmとなるように塗布した。塗布から10分間放置したところ、塗布面の表面に3次元模様が形成された。次に、塗布面を上にしたまま、コンベア付きのUV照射装置(UVランプとしてフュージョンHバルブを備える)を用いて、紫外線照射を行った。該紫外線照射により3次元模様を固定化し、シート表面に3次元模様を形成したポリマーシートを得た。
なお、紫外線照射は、コンベア速度3.5m/分で、コンベア付きのUV照射装置に5回通過させることにより行った。1回あたりのUV照度は290mW/cm2であり、1回あたりの光量は830mJ/cm2であった。
PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の一方の面に、実施例1と同様に、光重合性組成物(B)を、厚さが100μmとなるように塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
なお、光重合性組成物(B)と同じ組成のモノマー溶液(2−エチルヘキシルアクリレート:90重量部とアクリル酸:10重量部)の過剰量に、PET基材を25℃で浸漬したとき、PET基材は75秒後に初期重量の1.1倍、3日後に初期重量の1.1倍に重量増加した。
PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の一方の面に、実施例2と同様に、光重合性組成物(B)を、厚さが200μmとなるように塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の一方の面に、実施例3と同様に、光重合性組成物(B)を、厚さが400μmとなるように塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の一方の面に、実施例4と同様に、光重合性組成物(C)を、厚さが100μmとなるように塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
なお、光重合性組成物(C)と同じ組成のモノマー溶液(アクリル酸ブチル:100重量部)の過剰量に、PET基材を25℃で浸漬したとき、PET基材は75秒後に初期重量の1.1倍、3日後に初期重量の1.1倍に重量増加した。
PET基材(厚さ38μmの2軸延伸ポリエチレンテレフタレートフィルム、商品名「ルミラーS10」東レ社製)の一方の面に、実施例5と同様に、光重合性組成物(E)を、厚さが100μmとなるように塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
PET基材付きポリマーシート(C)のポリマーシート上に光重合性組成物(B)を厚さ200μmで塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
なお、光重合性組成物(B)と同じ組成のモノマー溶液(2−エチルヘキシルアクリレート:90重量部とアクリル酸:10重量部)の過剰量に、PET基材付きポリマーシート(C)から取り出したポリマーシートを25℃で浸漬したとき、ポリマーシートは75秒後に初期重量の3.8倍に重量増加したが、3日後にはほとんど溶解しており、初期重量の0.03倍まで重量減少した。
PET基材付きポリマーシート(D)のポリマーシート上に光重合性組成物(B)を厚さ50μmで塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
PET基材付きポリマーシート(E)のポリマーシート上に光重合性組成物(B)を厚さ50μmで塗布した。塗布から1時間経っても、塗布面の表面に3次元模様は形成されなかった。
実施例及び比較例について、目視や走査型電子顕微鏡(SEM)(装置名「S−4800」株式会社日立ハイテクノロジーズ製)により、表面構造や断面構造を観察した。その結果を図1~12に示した。
図2において、スケールの1目盛りは、100μmである。
図3において、スケールの1目盛りは、100μmである。
図4において、スケールの1目盛りは、100μmである。
図5において、スケールの1目盛りは、100μmである。
図6において、スケールの1目盛りは、100μmである。
図7において、スケールの1目盛りは、10μmである。
図8において、スケールの1目盛りは、50μmである。
図9において、スケールの1目盛りは、10μmである。
図10において、スケールの1目盛りは、0.5mmである。
図11において、スケールの1目盛りは、100μmである。
図12において、スケールの1目盛りは、50μmである。
Claims (7)
- ポリマーシートの片面上に、該ポリマーシートが吸収可能な少なくとも1種の重合性モノマーを含むモノマー混合物又はその部分重合物を必須成分とする重合性組成物を塗布し、表面形状を3次元的に変化させた後、重合硬化させて、表面に3次元模様を形成することを特徴とする表面に3次元模様を有するポリマーシートの製造方法。
- ポリマーシートの片面上に、該ポリマーシートが吸収可能な少なくとも1種の重合性モノマーを含むモノマー混合物又はその部分重合物を必須成分とする重合性組成物を塗布し、該塗布面にカバーフィルムを貼付することなく、表面形状を3次元的に変化させた後、重合硬化させる請求項1記載の3次元模様を有するポリマーシートの製造方法。
- ポリマーシートの片面上に重合性組成物を塗布してから重合に付すまでの時間が1分以上である請求項1又は2記載の3次元模様を有するポリマーシートの製造方法。
- 重合性組成物が、さらに、少なくとも1つのポリマーシートに吸収されない物質を含む請求項1~3の何れかの項に記載の3次元模様を有するポリマーシートの製造方法。
- ポリマーシート及び重合性組成物のいずれか又は両方が光重合開始剤を含んでいる請求項1~4の何れかの項に記載の3次元模様を有するポリマーシートの製造方法。
- 活性エネルギー線照射により重合硬化させる請求項1~5の何れかの項に記載の3次元模様を有するポリマーシートの製造方法。
- 活性エネルギー線が、紫外線である請求項6記載の3次元模様を有するポリマーシートの製造方法。
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JPH1134243A (ja) * | 1997-07-23 | 1999-02-09 | Oike Ind Co Ltd | 防眩性ハードコートフィルム |
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JPS59216662A (ja) * | 1983-05-23 | 1984-12-06 | Toppan Printing Co Ltd | 凹凸化粧材の製造方法 |
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GB2331717B (en) * | 1997-11-26 | 1999-12-22 | Ranier Ltd | Reticulated coatings |
JP4255943B2 (ja) * | 1998-07-14 | 2009-04-22 | 大日本印刷株式会社 | 化粧材 |
US20090169817A1 (en) * | 2006-06-02 | 2009-07-02 | Nitto Denko Corporation | Polymer articles with Polymer layer containing incompatible material unevenly distributed and surface-roughened tape or sheet comprising the polymer articles |
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JPH1134243A (ja) * | 1997-07-23 | 1999-02-09 | Oike Ind Co Ltd | 防眩性ハードコートフィルム |
JP2001290009A (ja) * | 2000-01-31 | 2001-10-19 | Nitto Denko Corp | 光拡散層、光拡散性シート及び光学素子 |
JP2008006817A (ja) * | 2006-06-02 | 2008-01-17 | Nitto Denko Corp | 非相溶性物質偏在ポリマー層を有するポリマー部材、及び該ポリマー部材からなる表面凹凸テープ又はシート |
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WO2010107095A1 (ja) * | 2009-03-17 | 2010-09-23 | 日東電工株式会社 | ポリマー部材の製造方法、及びポリマー部材 |
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