JP2010042589A - Sheet product and manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet product including a resin-made substrate sheet coated with an abrasion-resistant film, and a manufacturing method thereof, capable of forming the film with high adhesion strength. <P>SOLUTION: At least one surface of a cured product of a resin composition (C) is coated with a cured product of a resin composition (F). Resin composition (C): an active energy beam-curable resin composition which contains an urethane poly(meth)acrylate (A1) synthesized from an alicyclic polyisocyanate and a hydroxyalkyl(meth)acrylate, or a mixture of (A1) and the other monomer copolymerizable therewith; and a photopolymerization initiator. Resin composition (F): an active energy beam-curable resin composition which contains a cross-linking polymerizable compound (D1) having a molecular weight of 150 or more and at least two (meth)acryloyloxy groups, and differed from the urethane poly(meth)acrylate (A1), or a mixture of (D1) and the other monomer copolymerizable therewith; and a photopolymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sheet-like material excellent in scratch resistance obtained by forming a resin film with high adhesion strength on a sheet-like material obtained by curing using active energy rays, and a method for producing the same. .

  The active energy ray-curable resin composition does not require an organic solvent, and can give excellent properties such as toughness, flexibility, weather resistance, and chemical resistance to the cured product according to the composition. Furthermore, since the active energy ray-curable resin composition has a property of being cured in a short time by active energy rays and is generally excellent in transparency, its application to optical applications has recently been expanded.

  In recent years, in an electronic device such as a mobile phone or a digital camera, a resin-made transparent plate is increasingly used as a front plate for the purpose of protecting the display. However, for the purpose of protecting the display, if an active energy ray-curable resin composition that can be shaped into a sheet shape is used and a sheet-like material formed by polymerization and curing is used, the scratch resistance is not sufficient. There's a problem.

  As a method for imparting scratch resistance to a sheet-like material, it is well known to form a scratch-resistant film on the surface of a resin base material sheet-like material. As a method for forming a scratch-resistant film on the surface of a resin base material sheet, a method of directly coating the scratch-resistant film composition on the surface of a resin base sheet is known. As such a method, a method in which polyfunctional methacrylate or acrylate is used as a scratch-resistant coating composition and cured by irradiation with active energy rays to obtain a scratch-resistant coating is known as a method with good productivity. Yes.

  However, this method has a problem that the adhesion between the scratch-resistant film and the resin base sheet is low. In addition, when the resin base sheet is a resin having a crosslinked structure, in general, the adhesion to the film is lower than that of a resin base sheet formed from a resin having no crosslink structure. It is supposed to be. Furthermore, this method also has a problem that warpage occurs in the obtained sheet-like material due to volume shrinkage during curing of the scratch-resistant film.

In Patent Document 1, as a method for improving the adhesion between the resin base material sheet and the scratch-resistant film, an organic solvent is first applied to the surface of the resin base material sheet and then dried, A technique is disclosed in which a scratch-resistant coating composition is applied and then irradiated with active energy rays. However, since this method involves drying of the organic solvent, there is a problem that the facility becomes complicated and the productivity is lowered.
Japanese Patent Laid-Open No. 5-125198

  An object of the present invention is to provide a sheet material coated with a scratch-resistant film and a high adhesion strength to a resinous substrate sheet material produced by polymerization and curing by irradiation with active energy rays. It is providing the manufacturing method of the sheet-like material which can be formed.

The gist of the present invention is as follows.
At least one side of the cured product of the following resin composition (C) is in a sheet-like product coated with the cured product of the following resin composition (F).
[Resin composition (C)]
Component (A): urethane poly (meth) acrylate (A1) synthesized from alicyclic polyisocyanate and hydroxyalkyl (meth) acrylate, or the urethane poly (meth) acrylate (A1) and others copolymerizable therewith A mixture of monomers,
Component (B): An active energy ray-curable resin composition containing a photopolymerization initiator.
[Resin composition (F)]
Component (D): a crosslinkable compound (D1) having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups and different from the urethane poly (meth) acrylate (A1), or the crosslink polymerization A mixture of the active compound (D1) and other monomers copolymerizable therewith,
Component (E): Active energy ray-curable resin composition containing a photopolymerization initiator.

  The urethane poly (meth) acrylate (A1) is preferably a compound represented by the following formula (1).

(In Formula (1), R ¹ is an alicyclic diisocyanate residue, R ² is each independently an alkylene group, and R ³ is each independently a hydrogen atom or a methyl group.)
The gist of the present invention is as follows.
A method for producing the above sheet-like material,
Applying the resin composition (F) to the surface of a glass or metal mold and polymerizing and curing the resin composition (F) on the surface of the mold; and
A cured product of the resin composition (C) is formed by applying the resin composition (C) to a mold on which a cured product of the resin composition (F) is formed, and irradiating with active energy rays to polymerize and cure. And a step of integrating the cured product of the resin composition (F).

  A stainless steel plate having a mirror surface is preferably used as the mold. In this case, the resin composition (C) is applied to a stainless steel plate having the mirror surface, on which a cured product of the resin composition (F) is formed, and the resin composition is formed using a transparent glass plate or a transparent resin plate. It is preferable to polymerize and cure by irradiating active energy rays after coating the product (C). Furthermore, the resin composition (F) is applied in advance to the surface of the transparent glass plate or transparent resin plate that is in contact with the resin composition (C), polymerized and cured, and then made of the transparent glass. It is preferable to integrate the cured product of the resin composition (F) and the cured product of the resin composition (C) formed on a plate or a transparent resin plate.

  Moreover, it is preferable to use a stainless steel continuous belt having a mirror surface as the mold. In this case, the resin composition (C) is applied to the continuous belt made of stainless steel having the mirror surface and formed with a cured product of the resin composition (F), and is allowed to proceed, and at the same speed in the same direction relative thereto. It is preferable that the resin composition (C) is coated with a transparent resin film that progresses in step 1, and then polymerized and cured by irradiation with active energy rays. Further, the resin composition (F) is applied to the surface of the transparent resin film on the side in contact with the resin composition (C), polymerized and cured, and the resin composition formed on the transparent resin film. It is preferable to integrate the cured product of the product (F) and the cured product of the resin composition (C).

  In this specification, the notation “(meth) acryl” means acrylic or methacrylic. The same applies to other equivalent notations.

  According to the present invention, a sheet-like material coated with a scratch-resistant film is obtained with respect to a resin-made substrate sheet-like material produced by polymerization and curing by irradiation with active energy rays. Moreover, the sheet-like material which formed the film | membrane with high adhesive strength is obtained. As a result, it is possible to efficiently produce a high-quality and scratch-resistant sheet material.

<Component (A)>
Component (A) is urethane poly (meth) acrylate (A1) synthesized from alicyclic polyisocyanate and hydroxyalkyl (meth) acrylate, or urethane poly (meth) acrylate (A1) and copolymerizable therewith. It is a mixture of other monomers.

  The urethane poly (meth) acrylate (A1) serving as the component (A) is a component that imparts low shrinkage to the resin composition (C) and improves the flexibility of the resulting cured product. The urethane poly (meth) acrylate (A1) is preferably a compound represented by the following formula (1).

(In Formula (1), R ¹ is an alicyclic diisocyanate residue, R ² is each independently an alkylene group, and R ³ is each independently a hydrogen atom or a methyl group.)
Specific examples of the alicyclic polyisocyanate for synthesizing the urethane poly (meth) acrylate (A1) include alicyclic polyisocyanates having two or more isocyanate groups in the molecule. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-cyclohexyl diisocyanate. Furthermore, a polyisocyanate compound obtained by reacting these compounds with a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group, or water, or a trimer of the alicyclic polyisocyanate described above A pentamer or the like can also be used. 1 type can also be used for alicyclic polyisocyanate and it can also use 2 or more types together.

  Among these, 1,3-bis (isocyanatomethyl) cyclohexane is preferable from the viewpoint of workability during handling.

  Specific examples of hydroxyalkyl (meth) acrylate for synthesizing urethane poly (meth) acrylate (A1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Hydroxyl group-containing alkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate; monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl (meth) acrylate and ( An addition reaction product with (meth) acrylic acid is mentioned. One kind of hydroxyalkyl (meth) acrylate can be used, or two or more kinds can be used in combination.

  Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) in terms of low viscosity of the synthesized urethane poly (meth) acrylate (A1). Acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl acrylate are preferred.

  As a method for producing the urethane poly (meth) acrylate (A1), for example, the alicyclic polyisocyanate and the hydroxyalkyl (meth) acrylate are hydroxyalkyl (with respect to 1 equivalent of the isocyanate group of the alicyclic polyisocyanate. An example is a method in which an addition reaction is performed at a ratio of about 1 to 1.1 equivalents of hydroxyl groups of (meth) acrylate.

  The addition reaction between the alicyclic polyisocyanate and the hydroxyalkyl (meth) acrylate can be performed by a known method. For example, a mixture of a hydroxyalkyl (meth) acrylate or an alicyclic polyisocyanate and a catalyst such as di-n-butyric acid laurate is added to an alicyclic polyisocyanate or a hydroxyalkyl (meth) acrylate at 50 to 90 ° C. After dropping under conditions, urethane poly (meth) acrylate (A1) can be produced by further reacting for 6 to 12 hours.

  As the component (A), one type of urethane poly (meth) acrylate (A1) can be used, or two or more types can be used in combination.

  The component (A) may be only the urethane poly (meth) acrylate (A1), but if it is within a range that does not interfere with the effect of the resin composition (C), the component (A) and the urethane poly (meth) acrylate (A1) are the same. It may be a mixture with other polymerizable monomers. Examples of the other copolymerizable monomer used as component (A) include urethane (meth) acrylates other than urethane poly (meth) acrylate (A1), polyfunctional oligomers, polyfunctional monomers, and monofunctionals. Monomers, polymers thereof, and the like can be used. 1 type can also be used for the other monomer which can superpose | polymerize, and it can also use 2 or more types together.

  Specific examples of urethane (meth) acrylates other than urethane poly (meth) acrylate (A1) include urethane (meth) acrylate synthesized from non-alicyclic polyisocyanate and hydroxyalkyl (meth) acrylate; alicyclic or Examples thereof include urethane (meth) acrylate synthesized from non-alicyclic polyisocyanate, polyol and hydroxyalkyl (meth) acrylate.

  Specific examples of the polyfunctional oligomer include epoxy (meth) acrylate and polyester (meth) acrylate.

  Specific examples of the polyfunctional monomer include tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis (acryloxyethyl) isocyanurate, tris (acryloxyethyl) isocyanurate, Examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.

  Specific examples of the monofunctional monomer include monoethylenically unsaturated compounds such as (meth) acrylic acid and esters thereof, (meth) acrylonitrile, styrene and derivatives thereof. Of these, hydroxyalkyl (meth) acrylate is preferred.

  Specific examples of the hydroxyalkyl (meth) acrylate as the monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Hydroxyl group-containing alkyl (meth) acrylates such as butyl (meth) acrylate and 6-hydroxyhexyl acrylate; monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether and glycidyl (meth) acrylate and (meth) acrylic acid An addition reaction product is mentioned.

  Among these, in order to lower the viscosity of the resulting composition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta ) Hydroxyl group-containing alkyl (meth) acrylates such as acrylates are preferred.

  The amount of the other copolymerizable monomer is preferably 10 to 60 parts by mass in 100 parts by mass of the component (A). When the blending amount of the other copolymerizable monomer is 10 parts by mass or more, the viscosity of the resin composition (C) becomes appropriate, and the workability during handling tends to be improved. Further, by setting the other copolymerizable monomer to 60 parts by mass or less, it is possible to reduce the warpage of the substrate when the resin composition (C) is applied and cured on the substrate. Moreover, the more preferable compounding quantity of the said copolymerizable other monomer which exists in the tendency which can provide sufficient hardness to hardened | cured material is 20-40 mass parts.

<Component (B)>
Component (B) is a photopolymerization initiator and is a component for efficiently curing the resin composition (C) by irradiation with active energy rays.

  Specific examples of the photopolymerization initiator as the component (B) include those that generate a radical source mainly in response to ultraviolet rays having a wavelength of 200 to 400 nm. Specific examples of the photopolymerization initiator as the component (B) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-di- Carbonyl compounds such as ethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; tetramethylthiuram Sulfur compounds such as monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-tri Acylphosphine oxides such as chill pentyl phosphine oxide. 1 type can also be used for the photoinitiator as a component (B), and it can also use 2 or more types together.

  Among these, benzoin monomethyl ether, benzophenone, benzoin isopropyl ether, methyl phenylglyoxylate, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal and 2,4,6 in terms of the balance between the hardness and curling property of the cured product. -Trimethylbenzoyldiphenylphosphine oxide is preferred.

<Resin composition (C)>
The resin composition (C) is an active energy ray-curable resin composition containing the component (A) and the component (B).

  The blending amount of component (B) is preferably 0.005 to 5 parts by mass, more preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of component (A). Curing tends to be sufficient when the blending amount of component (B) is 0.005 parts by mass or more, and transparency and toughness of the cured product tend to be ensured by being 5 parts by mass or less. .

  In the resin composition (C), an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent, a pigment, an anti-settling agent are added as necessary within the range that does not interfere with the effect of the resin composition (C). Various additives such as an agent, an antifoaming agent, an antistatic agent, and an antifogging agent can be blended.

<Component (D)>
Component (D) has a molecular weight of 150 or more and has at least two (meth) acryloyloxy groups, and is a crosslinkable polymerizable compound (D1) different from the urethane poly (meth) acrylate (A1), or the crosslinks It is a mixture of a polymerizable compound (D1) and other monomers copolymerizable therewith.

  The crosslinkable compound (D1) serving as the component (D) is a compound having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups. However, the crosslinkable compound (D1) does not include a compound that becomes urethane poly (meth) acrylate (A1). These groups are preferably bonded with a residue composed of an aliphatic hydrocarbon group or a derivative thereof (for example, a saturated aliphatic hydrocarbon group bonded with an ether bond). The molecular weight is preferably 300 or more, and preferably 3000 or less. 1 type can also be used for a crosslinking | crosslinked polymeric compound (D1), and it can also use 2 or more types together.

  Specific examples of the cross-linkable polymerizable compound (D1) include esterified products obtained from polyhydric alcohol and (meth) acrylic acid or derivatives thereof, polyhydric alcohol, polyvalent carboxylic acid and (meth) acrylic acid or derivatives thereof. An esterified product obtained from

  The esterified product obtained from polyhydric alcohol and (meth) acrylic acid or a derivative thereof is reacted with a mixture in which the hydroxyl group of polyhydric alcohol and the carboxyl group of (meth) acrylic acid are finally equivalent. Can be obtained. Specific examples of the esterified product obtained from polyhydric alcohol and (meth) acrylic acid or derivatives thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acryltrimethylolpropane triacrylate, pentaglycerol triacrylate and the like.

  Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 300 to about 1,000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1, 3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol) Dihydric alcohols such as 2-ethylhexyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedimethanol; trimethylolpropane (1,1,1-trimethylolpropane), pentaglycerol (1,1, -Trivalent alcohols such as trimethylolethane, glycerol, 1,2,4-butanetriol, 1,2,6-hexatriol; pentaerythritol (2,2-bishydroxymethyl-1,3-propanediol), di Examples of the alcohol include tetravalent or higher alcohols such as glycerol and dipentaerythritol.

  The esterified product obtained from polyhydric alcohol, polycarboxylic acid, and (meth) acrylic acid or derivatives thereof is finally composed of the hydroxyl group of polyhydric alcohol and the carboxyl group of both polyhydric carboxylic acid and (meth) acrylic acid. Can be obtained by reacting a mixture in an equivalent amount. As a preferable compound, an ester compound obtained by using a divalent alcohol or a trivalent alcohol or a mixture of a divalent alcohol and a trivalent alcohol as the polyhydric alcohol and using the divalent carboxylic acid as the polyvalent carboxylic acid. Is mentioned. When a mixture of a divalent alcohol and a trivalent alcohol is used as the polyhydric alcohol, the molar ratio can be arbitrarily selected. The molar ratio of divalent carboxylic acid to (meth) acrylic acid is such that the equivalent ratio of the carboxyl group of divalent carboxylic acid to the carboxyl group of (meth) acrylic acid is 2: 1 to 0: 1. preferable. By setting the amount of the divalent carboxylic acid within the above range, the viscosity of the ester to be produced is lowered and the formation of the coating film is facilitated.

  Specific examples of the divalent carboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sedicic acid; alicyclic dicarboxylic acids such as tetrahydrophthalic acid and 3,6-endomethylenetetrahydrophthalic acid; phthalic acid and isophthalic acid Aromatic dicarboxylic acids such as acid and terephthalic acid; thiodiglycolic acid, thiodivaleric acid, diglycolic acid, maleic acid, phthalic acid, itaconic acid, or chlorides, anhydrides and esters thereof can be used.

  The component (D) may be only the cross-linkable polymerizable compound (D1), but may be a mixture of the cross-linkable polymerizable compound (D1) and other monomers copolymerizable therewith. However, the component (D) preferably contains 30% by mass or more of the crosslinkable polymerizable compound (D1) with respect to 100% by mass of the resin composition (F). The content of the crosslinkable polymerizable compound (D1) is more preferably 40% by mass or more and preferably 70% by mass or less with respect to 100% by mass of the resin composition (F).

  Examples of the other copolymerizable monomer that is the component (D) include polyfunctional oligomers other than the crosslinkable polymerizable compound (D1), polyfunctional monomers, monofunctional monomers, and the like. Can be used. As the other copolymerizable monomer, one type may be used, or two or more types may be used in combination.

  Specific examples of the monofunctional monomer include monoethylenically unsaturated compounds such as (meth) acrylic acid and esters thereof, (meth) acrylonitrile, styrene and derivatives thereof.

<Ingredient (E)>
Component (E) is a photopolymerization initiator, which is a compound that is activated by light irradiation to generate radicals.

  Specific examples of the photopolymerization initiator as the component (E) include those exemplified as the aforementioned component (B). 1 type can also be used for the photoinitiator as a component (E), and it can also use 2 or more types together.

  Among these, benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal and 2 are considered from the balance of considering reactivity, weather resistance of the cured product and yellowing. , 4,6-Trimethylbenzoyldiphenylphosphine oxide is preferred.

<Resin composition (F)>
Resin composition (F) is an active energy ray-curable resin composition containing component (D) and component (E).

  The compounding amount of the component (E) is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (D). By setting the blending amount of component (E) to 0.1 parts by mass or more, the curing speed is increased, and the cumulative amount of ultraviolet light necessary for curing may be reduced. On the other hand, when the blending amount of component (E) is 20 parts by mass or less, the weather resistance of the formed film is improved, and the scratch resistance is also improved.

  In the resin composition (F), an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent, a pigment, an anti-settling agent are added as necessary within the range not impeding the effect of the resin composition (F). Various additives such as an agent, an antifoaming agent, an antistatic agent, and an antifogging agent can be blended.

<Sheet>
The sheet-like product of the present invention is a sheet-like product in which at least one surface of the cured product of the resin composition (C) is coated with the cured product of the resin composition (F).

  The cured product of the resin composition (C) is a part serving as a base material. The thickness of the cured product of the resin composition (C) is preferably 0.2 to 3.0 mm, and more preferably 0.4 to 1.5 mm.

  The cured product of the resin composition (F) is a portion that imparts scratch resistance to the substrate, and is preferably a film. 5-50 micrometers is preferable and, as for the thickness of the hardened | cured material of a resin composition (F), 10-30 micrometers is more preferable.

<Method for producing sheet-like material>
The method for producing the sheet-like product of the present invention comprises:
Applying the resin composition (F) to the surface of a glass or metal mold and polymerizing and curing the resin composition (F) on the surface of the mold; and
A cured product of the resin composition (C) is formed by applying the resin composition (C) to a mold on which a cured product of the resin composition (F) is formed, and irradiating with active energy rays to polymerize and cure. And a step of integrating the cured product of the resin composition (F).

  As the mold, glass or metal can be used. Specific examples of the material constituting the mold include inorganic glass such as tempered glass, stainless steel, aluminum, and metal plated with chromium. The surface of a mold such as inorganic glass or metal is generally a mirror surface, but in some cases, a surface that has been subjected to a matte treatment with fine irregularities on the surface can be used as appropriate. Among these, it is preferable to use a stainless steel plate having a mirror surface or a stainless steel continuous belt.

  Specific examples of the method for applying the resin composition (F) to the mold surface include a roller coating method, a bar coating method, a spray coating method, an air knife coating method, and a dipping method. Among these, the roll coating method is preferable because it is easy to control the accuracy of the application width of the resin composition (F).

  Polymerization and curing of the applied resin composition (F) can be performed by irradiating active energy rays such as ultraviolet rays. Specific examples of the ultraviolet irradiation lamp used for polymerization curing include a fluorescent chemical lamp, a mercury lamp, a metal halide lamp, and an arc lamp. The polymerization and curing of the resin composition (F) is preferably performed to such an extent that the resin composition (C) is not swelled or dissolved by the resin composition (C) to be applied later.

  Moreover, after apply | coating the resin composition (F) to the surface of a casting_mold | template, as a cover film, the organic polymer film which has no affinity with a resin composition (F) was stuck on it, and oxygen in the air was interrupted | blocked. A method in which the resin composition (F) is polymerized and cured and then only the organic polymer film is peeled off is preferable. Specific examples of the organic polymer film used as the cover film include films of polyester, polypropylene, moisture-proof cellophane, cellophane, polyethylene, polyvinyl chloride, polyvinyl alcohol, and the like.

  When the cover film is peeled off, the cured film of the resin composition (F) adheres to the cover film and may be removed from the mold. It is effective to perform curing in a state where the film is coated, and subsequently to cure the second stage of the film in the air after peeling the cover film from the film.

  Specific examples of the method for applying the resin composition (C) to the mold on which the cured product of the resin composition (F) is formed include a roller coating method, a bar coating method, an air knife coating method, and a dipping method. .

  Polymerization and curing of the applied resin composition (C) is performed by irradiating active energy rays such as ultraviolet rays. Specific examples of the ultraviolet irradiation lamp used for polymerization curing include a fluorescent chemical lamp, a mercury lamp, a metal halide lamp, and an arc lamp.

  In addition, after the resin composition (C) is applied, the resin composition (C) is polymerized and cured after being covered with a cover body that is transparent to active energy rays such as a transparent resin plate or a transparent glass plate. Is preferred. Examples of the cover include a film made of polyester, polypropylene, or polyvinyl chloride, a sheet made of acrylic resin, polyester, polypropylene, polyethylene, or polyvinyl chloride, or inorganic glass that has been reinforced. Of these, polyester (polyethylene terephthalate) films, acrylic resin sheets, and reinforced inorganic glass are preferred.

  Furthermore, it is preferable that the resin composition (F) is applied in advance to the surface of the cover body on the side in contact with the resin composition (C) and then polymerized and cured. The application and polymerization curing of the resin composition (F) can be performed by the same method as described above. The polymerization and curing of the resin composition (F) is preferably performed to such an extent that it does not swell or dissolve when it comes into contact with the resin composition (C).

  By doing so, the cured product of the resin composition (C) and the cured product of the resin composition (F) can be integrated, and at least one side of the cured product of the resin composition (C) is a resin composition. A sheet-like material coated with the cured product (F) is obtained.

  In this invention, in order to improve productivity, it is preferable to produce continuously using an endless belt. As a specific example of this method, the resin composition (C) is applied to a stainless steel continuous belt having a mirror surface on which a cured product of the resin composition (F) is formed. A method of polymerizing and curing by irradiating an active energy ray after covering the resin composition (C) with a transparent resin film proceeding at a speed can be mentioned. In this case, a method in which the resin composition (F) is applied in advance to the surface of the transparent resin film on the side in contact with the resin composition (C) and polymerized and cured may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these do not limit this invention. In the following description, “part” is based on mass.

[Preparation of resin composition (F)]
As component (D), 50 parts of a compound obtained by condensing trimethylolethane / succinic acid / acrylic acid in a molar ratio of 2/4 and 50 parts of 1,6-hexanediol diacrylate, and as component (E), photopolymerization The resin composition (F) was obtained by mixing 1.5 parts of benzoin methyl ether which is an initiator.

[Preparation of Resin Composition (C)]
As component (A), 80 parts of urethane diacrylate (A1) obtained by reacting 1,3-bis (isocyanatomethyl) cyclohexane / 2-hydroxypropyl acrylate at a molar ratio of 1/2 and 4-hydroxybutyl As a component (B), 20 parts of acrylate and 1 part of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed and stirred at room temperature to obtain a resin composition (C).

[Adhesion test]
Evaluation of the adhesion of the resin film to the base resin was carried out by the following test in accordance with JIS K5600-5-6. Cross cuts (cross cuts) reaching the base material at intervals of 1 mm were put in the cured film, 100 100 square cuts of 1 mm ² were made, cellophane tape was stuck on them and peeled off rapidly, and the peeled cross cuts were counted. The case where there was no separation was indicated by ◯, the case where the number of separations was 1 to 50, and the case where the number of separations was 51 to 100.

[Example 1]
A resin composition (F) is applied on the mirror surface of a stainless steel plate (hereinafter referred to as “SUS plate”) having a size of 30 cm × 30 cm, and on the mirror surface of the SUS plate coated with this resin composition (F). A polyethylene terephthalate film (hereinafter referred to as PET film) is covered so as not to contain air bubbles, and the excess resin composition (F) is squeezed using a rubber roll so that the thickness of the resin composition (F) layer becomes 20 μm. I put it out. Next, the surface of the SUS plate coated with the resin composition (F) is faced up, and 20 cm below the ultraviolet irradiation device in which 20 fluorescent UV lamps (product name: FL40BL, manufactured by Toshiba Lighting & Technology) are arranged in parallel. The position is 3 m / min. So as to be perpendicular to the longitudinal direction of the fluorescent ultraviolet lamp. The resin composition (F) was cured by passing at a speed of. Thereafter, only the layer of the resin composition (F) was left on the SUS plate, and only the PET film was peeled off. Next, with the surface of the SUS plate on which the layer of the resin composition (F) was formed facing upward, a position 20 cm below the high-pressure mercury lamp with an output of 120 W / cm was 3 m / min. The resin composition (F) was further cured by passing it at a speed of 20 μm to obtain a cured coating film (resin film) having a thickness of 20 μm.

  A gasket made of soft polyvinyl chloride was installed on the four sides of the SUS plate thus formed with the resin film, and used as a spacer between the SUS plate and the cover body to be covered later. The resin composition (C) is injected from the center of the SUS plate and covered with an inorganic glass plate (hereinafter referred to as “glass plate”) having a thickness of 8 mm and subjected to a strengthening process having a size of 30 cm × 30 cm. The spacing between the facing surfaces of the SUS plate and the glass plate was 0.8 mm. With the glass plate face up, the position 20 cm below the high-pressure mercury lamp with an output of 120 W / cm is 3 m / min. The resin composition (C) was cured by passing it at a speed of 1 to obtain a base resin.

  When the base resin thus formed was peeled off from the SUS plate and the glass plate, which were the molds, the cured coating film formed on the mold was all transferred to the base resin, and one side was coated with the resin film. A resin sheet having a thickness of 0.7 mm was obtained. The evaluation results of the obtained resin sheet are shown in Table 1.

[Example 2]
A glass plate having a resin film with a thickness of 20 μm was obtained in the same manner as in Example 1 except that the SUS plate was a glass plate of the same size.

  Example 1 except that the glass plate thus formed with the resin film was used as a cover body for the resin composition (C) such that the side on which the resin film was formed was in contact with the resin composition (C). In the same manner, the resin composition (C) was cured to obtain a base resin. When the base resin thus formed was peeled off from the SUS plate and the glass plate, which were the molds, the cured coating film formed on the mold and the cover body was all transferred to the base resin, and both sides were covered with the resin film. A resin sheet having a thickness of 0.7 mm was obtained. The evaluation results of the obtained resin sheet are shown in Table 1.

[Example 3]
A 0.7 mm-thickness coated with a resin film on both sides in the same manner as in Example 2 except that a PMMA plate (Mitsubishi Rayon Co., Ltd., trade name: Acrylite L) was used instead of the glass plate. A resin sheet was obtained. The evaluation results of the obtained resin sheet are shown in Table 1.

[Example 4]
A SUS endless belt 9 having a mirror-finished thickness of 1 mm and a width of 1500 mm in the apparatus shown in FIG. 1 and a PET film (P1) 1 having a thickness of 188 μm in parallel and in the same direction at a speed of 3.0 m / min. Was run. The PET film (P1) 1 is provided with a resin film forming device 10 in the horizontal section formed on the upper part of the SUS endless belt 9, and the SUS endless belt 9 is provided in the horizontal section.

  The PET film (P1) 1 is a horizontal section formed on the upper part of a SUS endless belt 9, and the SUS endless belt 9 is a SUS endless resin composition (F) 4 in the horizontal section using a metering pump. The film is dropped onto the belt surface and the PET film (P1) surface, and a PET film (P2) 2 having a thickness of 12 μm is adhered onto the belt surface and the PET film (P1) surface by the press roll 7 at the same speed as the belt traveling speed. The resin film was uniformly applied so that the thickness of the resin film was 20 μm so that no bubbles remained between the endless belt 9 and the PET film (P1) 1 and the PET film (P2) 2. The PET film (P2) 2 was continuously supplied by an unwinding roll 8. With the PET film (P2) 2 in close contact, the SUS endless belt 9 and the PET film (P1) 1 are passed through the same ultraviolet irradiation device (fluorescent ultraviolet lamp 5) as in Example 1 and applied between them. A resin film was obtained.

  Thereafter, only the PET film (P2) was peeled off and taken up on a take-up roll, leaving only the resin film on the belt surface. In order to seal the both sides between the belt surfaces treated with resin film, two hollow pipes made of polyvinyl chloride are installed as gaskets, and the space formed by the gasket, the SUS endless belt 9 and the PET film (P1) 1 is installed. The resin composition (C) 3 was supplied through an injection device by a metering pump. The resin composition (C) was polymerized and cured by placing the high-pressure mercury lamp 6 having an output of 120 W / cm described in Example 1 20 cm away from the belt surface and irradiating it with ultraviolet rays. When the resin plate was peeled off from the SUS endless belt 9 and the PET film (P1) 1, the resin film was completely transferred to the base resin, and both sides were coated with a resin film having a thickness of 0.7 mm. Sheets were obtained continuously. The evaluation results of the obtained resin sheet are shown in Table 1.

[Comparative Example 1]
Instead of the resin composition (C), 1-hydroxy which is a photopolymerization initiator is used for 100 parts of a mixture of a methyl methacrylate and a partial polymer of methyl methacrylate (viscosity 1000 cp (20 ° C., polymerization rate 20%)). A resin sheet having a resin film was prepared in the same manner as in Example 1 except that 1 part of cyclohexyl phenyl ketone was mixed and stirred as the resin composition (G). However, a layer of the resin composition (G) formed on a SUS plate with a resin film formed and covered with a glass plate was passed under a high-pressure mercury lamp, but it was not polymerized and cured, and a sheet-like material was formed. There wasn't.

  Furthermore, although it passed under the high pressure mercury lamp 9 times, it was not fully polymerized and cured, and a sheet-like material was not formed.

  The sheet-like material of the present invention has excellent scratch resistance and is suitable for various uses such as a display front plate.

It is the schematic which shows an example of the manufacturing apparatus of the sheet-like material of this invention.

Explanation of symbols

1 PET film (P1)
2 PET film (P2)
3 Resin composition (C)
4 Resin composition (F)
DESCRIPTION OF SYMBOLS 5 Fluorescent ultraviolet lamp 6 High pressure mercury lamp 7 Press roll 8 Unwinding roll 9 SUS endless belt 10 Resin film formation apparatus

Claims (11)

A sheet-like product in which at least one surface of a cured product of the following resin composition (C) is coated with a cured product of the following resin composition (F).
[Resin composition (C)]
Component (A): urethane poly (meth) acrylate (A1) synthesized from alicyclic polyisocyanate and hydroxyalkyl (meth) acrylate, or urethane poly (meth) acrylate (A1) and others copolymerizable therewith A mixture of monomers,
Component (B): An active energy ray-curable resin composition containing a photopolymerization initiator.
[Resin composition (F)]
Component (D): Crosslinkable polymerizable compound (D1) having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups and different from the urethane poly (meth) acrylate (A1), or the crosslinkable polymer A mixture of the active compound (D1) and other monomers copolymerizable therewith,
Component (E): Active energy ray-curable resin composition containing a photopolymerization initiator. The sheet-like material according to claim 1, wherein the urethane poly (meth) acrylate (A1) is a compound represented by the following formula (1).

(In Formula (1), R ¹ is an alicyclic diisocyanate residue, R ² is each independently an alkylene group, and R ³ is each independently a hydrogen atom or a methyl group.) A method for producing the sheet-like material according to claim 1 or 2,
Applying the resin composition (F) to the surface of a glass or metal mold and polymerizing and curing the resin composition (F) on the surface of the mold; and
A cured product of the resin composition (C) is formed by applying the resin composition (C) to a mold on which a cured product of the resin composition (F) is formed, and irradiating with active energy rays to polymerize and cure. And a process for integrating the cured product of the resin composition (F).   The manufacturing method of the sheet-like object of Claim 3 using the stainless steel board which has a mirror surface as the said casting_mold | template.   The manufacturing method of the sheet-like object of Claim 3 using the stainless steel continuous belt which has a mirror surface as the said casting_mold | template.   The resin composition (C) is applied to a stainless steel plate having a mirror surface, on which a cured product of the resin composition (F) is formed, and the resin composition (C) is covered with a transparent glass plate The method for producing a sheet-like material according to claim 4, wherein the composition is cured by irradiation with active energy rays.   The resin composition (C) is applied to a stainless steel plate having the mirror surface, on which a cured product of the resin composition (F) is formed, and the resin composition (C) is covered with a transparent resin plate. The method for producing a sheet-like material according to claim 4, wherein the composition is cured by irradiation with active energy rays.   The resin composition formed on the transparent glass plate by applying the resin composition (F) to the surface of the transparent glass plate on the side in contact with the resin composition (C), polymerizing and curing in advance. The manufacturing method of the sheet-like material of Claim 6 integrated with the hardened | cured material of a thing (F) and the hardened | cured material of the said resin composition (C).   The resin composition formed on the transparent resin plate by applying the resin composition (F) in advance to the surface of the transparent resin plate on the side in contact with the resin composition (C), followed by polymerization and curing. The manufacturing method of the sheet-like material of Claim 7 integrated with the hardened | cured material of a thing (F) and the hardened | cured material of the said resin composition (C).   The resin composition (C) is applied to the stainless steel continuous belt having the mirror surface, on which the cured product of the resin composition (F) is formed, and is allowed to proceed, and proceeds in the same direction and at the same speed. The method for producing a sheet-like product according to claim 5, wherein the resin composition (C) is coated with a transparent resin film and then polymerized and cured by irradiation with active energy rays.   The resin composition (F) is applied to the surface of the transparent resin film on the side in contact with the resin composition (C), polymerized and cured in advance, and the resin composition ( The manufacturing method of the sheet-like material of Claim 10 integrated with the hardened | cured material of F) and the hardened | cured material of the said resin composition (C).

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