JP2012050941A - Method for production of laminated sheet roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet roll in which appearance defects such as gauge band, wrinkle, slack or irregular winding are inhibited to exert favorable printing characteristics, and to provide a method for production thereof.SOLUTION: The method for production of a laminated sheet roll includes the steps of: applying a mixed solution comprising a resin composition (A) and a solvent (S) onto an acrylic resin substrate sheet (B); heating and drying the acrylic resin substrate sheet (B) for volatilizing the solvent (S) to form the layer of the resin composition (A) on the sheet (B); and winding a laminated sheet including the resin composition (A) and the sheet (B). The elongation percentage (L) at heat drying of the acrylic resin substrate sheet (B) is ≥0.001% but ≤0.5%, and the tension (F2) per unit width of the laminated sheet when winded is ≥60 N/m but ≤170 N/m.

Description

  The present invention relates to a method for producing a laminated sheet roll in which a resin composition layer is laminated on an acrylic resin base sheet. In particular, the laminated sheet roll has improved appearance defects such as gauge bands, wrinkles, sagging and roll-off, and the unrolled laminated sheet has excellent appearance, design, wear resistance, chemical resistance and weather resistance. A sheet roll can be provided.

  Acrylic resin base sheet is used by bonding to the surface of various resin base materials, glass, metal, wood, cloth, etc., taking advantage of its excellent weather resistance, transparency and processability, It is applied to designability. Various studies have been conducted for the purpose of improving the printing characteristics of the acrylic resin base sheet and improving the appearance defects such as roll-up and wrinkle. (For example, Patent Documents 1 to 3).

  However, in the said patent document, although the manufacturing method of the acrylic resin base material sheet itself is disclosed, in a later step, a laminate in which a resin composition layer is further laminated on the acrylic resin base material sheet by a method such as coating. There is no disclosure of a sheet manufacturing method.

  On the other hand, a method for producing a photocurable sheet in which a photocurable resin composition layer is laminated on an acrylic resin base sheet has been proposed (for example, Patent Document 4). According to this method, it is possible to suppress the occurrence of cracks in the photocurable resin composition layer and loosening and wrinkles during the conveyance of the photocurable sheet. However, appearance defects such as gauge bands, wrinkles, sagging, and collapse may occur in the laminated sheet roll after winding, and there is room for further study.

JP 2008-230722 A JP 2010-30202 A JP 2010-30756 A JP 2003-285006 A

  An object of the present invention is to provide a laminated sheet roll having excellent printing characteristics while suppressing appearance defects such as gauge bands, wrinkles, sagging, and winding collapse.

  The method for producing a laminated sheet roll according to the present invention includes a step of applying a mixed solution containing a resin composition (A) and a solvent (S) on an acrylic resin base sheet (B), and an acrylic resin base sheet. The step of volatilizing the solvent (S) by heating and drying (B) to form the resin composition (A) layer on the acrylic resin substrate sheet (B), the resin composition (A) layer, and the acrylic resin A step of winding a laminated sheet containing the base sheet (B), and a method for producing a laminated sheet roll comprising the acrylic resin base sheet (B) calculated by the following formula (1): ) Is 0.001% or more and 0.5% or less, and the tension (F2) per unit width of the laminated sheet during winding of the laminated sheet is 60 N / m or more and 170 N / One characterized by m or less It is.

L = [F1 / (E * t * W)] * 100 (1)
(In the formula (1), F1: tension (N) applied to the acrylic resin base sheet (B) at the time of heat drying, E: flow direction (MD direction) of the acrylic resin base sheet (B) at the time of heat drying Tensile elastic modulus (MPa), t: thickness (mm) of the acrylic resin base sheet (B), W: width (mm) of the acrylic resin base sheet (B).

  According to the method of the present invention, it is possible to produce a laminated sheet roll having good printing characteristics in which appearance defects such as gauge bands, wrinkles, sagging, and winding are suppressed, and printing is less likely to occur when printing is performed. Can do.

  The method for producing a laminated sheet roll according to the present invention includes a step of applying a mixed solution containing a resin composition (A) and a solvent (S) on an acrylic resin base sheet (B), and an acrylic resin base sheet. The step of volatilizing the solvent (S) by heating and drying (B) to form the resin composition (A) layer on the acrylic resin substrate sheet (B), the resin composition (A) layer, and the acrylic resin A step of winding a laminated sheet containing the base sheet (B), and a method for producing a laminated sheet roll comprising the acrylic resin base sheet (B) calculated by the following formula (1): ) Is 0.001% or more and 0.5% or less, and the tension (F2) per unit width of the laminated sheet during winding of the laminated sheet is 60 N / m or more and 170 N / One characterized by m or less It is.

L = [F1 / (E * t * W)] * 100 (1)
(In Formula (1), F1: tension (N) applied to the acrylic resin base sheet (B) during heat drying, E: tensile elastic modulus in the flow direction of the acrylic resin base sheet (B) during heat drying ( MPa), t: thickness (mm) of acrylic resin base sheet (B), W: width (mm) of acrylic resin base sheet (B). Thereby, appearance defects such as gauge bands, wrinkles, sagging, and collapse of the laminated sheet roll can be improved.

<Mixed solution application process>
In the method according to the present invention, a mixed solution containing the resin composition (A) and the solvent (S) is applied onto the acrylic resin substrate sheet (B). As a coating method, for example, a mixed solution obtained by sufficiently stirring and dissolving the resin composition (A) in the solvent (S) is used for a known printing method such as a gravure printing method, a screen printing method, an offset printing method, or blade coating. Acrylic coating by a known coating method such as a coating method, rod coating method, roll doctor coating method, knife coating method, comma coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, dip coating method, etc. The method of apply | coating on a resin base material sheet (B) is mentioned. In addition, the method according to the present invention includes this step, a step of performing heat drying for removing the solvent (S) described later to form a resin composition (A) layer, and a step of winding up the laminated sheet. The roll-to-roll method can be used.

[Resin composition (A)]
The resin composition (A) is laminated on the acrylic resin base sheet (B) as a resin composition (A) layer, and is scratch resistant, abrasion resistant, water resistant, chemical resistant, weather resistant, etc. Is used to impart the above properties to the surface of the acrylic resin substrate sheet (B). The resin composition (A) can be a thermoplastic resin composition, a thermosetting resin composition, a photocurable resin composition, or the like as long as the laminated sheet on which the resin composition (A) is laminated can be wound into a roll. Any resin composition can be appropriately selected from the above. These may use only 1 type and may use 2 or more types together.

  The thermoplastic resin composition is not particularly limited. For example, ABS (acrylonitrile / butadiene / styrene copolymer) resin, AS (acrylonitrile / styrene copolymer) resin, vinyl chloride resin, polystyrene resin, Polyolefin resins such as polypropylene, fluorine resins, cellophane resins, cellulose resins, polyurethane resins, polyamide resins such as nylon, polyester resins, polycarbonate resins, polyvinyl alcohol resins, ethylene vinyl alcohol resins, soft Examples thereof include resin compositions containing known thermoplastic resins such as acrylic resins or mixtures thereof.

  The thermosetting resin composition is not particularly limited. For example, epoxy resin, polyimide resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, urethane resin, etc. Resin composition containing a functional resin or a mixture thereof.

  As a photocurable resin composition, the resin composition containing the compound which has a photopolymerizable group in a molecule | numerator is mentioned. Examples of the photopolymerizable group include polymerizable groups such as an epoxy group, a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group.

  Among the resin compositions, the resin composition (A) is preferably a photocurable resin composition from the viewpoint of productivity. Moreover, it is a resin composition containing the acrylic resin (a-1) which has a radically polymerizable unsaturated group in a side chain from viewpoints of transparency, a weather resistance, abrasion resistance, the adhesiveness of the lamination sheet surface, etc. It is more preferable.

  The resin composition (A) is blended with additives such as a sensitizer, a modifying resin, a dye, a pigment, a leveling agent, a repellency inhibitor, an ultraviolet absorber, a light stabilizer, and an oxidation stabilizer as necessary. be able to. The sensitizer is a compound that accelerates the curing reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone. As the ultraviolet absorber, a known compound can be used, and either an organic ultraviolet absorber or an inorganic ultraviolet absorber can be used. However, it is preferable to use an organic ultraviolet absorber from the viewpoint of transparency.

[Acrylic resin (a-1) having radically polymerizable unsaturated group in side chain]
As an acrylic resin (a-1) which has a radically polymerizable unsaturated group in a side chain, the polymer which introduce | transduced the radically polymerizable unsaturated group into the polymer which homopolymerized or copolymerized the monomer is mentioned, for example. It is done.

  Examples of the monomer include N-methylol acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Monomers having a hydroxyl group such as acrylate, monomers having a carboxyl group such as (meth) acrylic acid, acryloyloxyethyl monosuccinate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate Monomers having an epoxy group such as 2-aziridinylethyl (meth) acrylate, monomers having an aziridinyl group such as allyl 2-aziridinylpropionate, (meth) acrylamide, diacetone acrylamide, dimethylamino Ethyl (meta Monomers having amino groups such as acrylate, diethylaminoethyl (meth) acrylate, monomers having sulfone groups such as 2-acrylamido-2-methylpropanesulfonic acid, 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate The adduct of a radically polymerizable monomer having diisocyanate and active hydrogen, such as an equimolar adduct, and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. These may use only 1 type and can also use 2 or more types together. Furthermore, in order to adjust the glass transition temperature (Tg) of the polymer of these monomers and to adjust the physical properties of the laminated sheet, the monomer and a monomer copolymerizable with the monomer are used. A monomer can also be copolymerized. Examples of the copolymerizable monomer include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N-phenylmaleimide, cyclohexylmaleimide, N- Examples thereof include imide derivatives such as butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene. These may use only 1 type and can also use 2 or more types together.

Next, a radically polymerizable unsaturated group can be introduced into a polymer obtained by homopolymerizing or copolymerizing the monomer by, for example, the following method.
(I) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.
(Ii) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the monomer having a hydroxyl group is subjected to a condensation reaction.
(Iii) In the case of a polymer or copolymer of a monomer having the epoxy group, isocyanate group or aziridinyl group, the monomer having a hydroxyl group or the monomer having a carboxyl group is subjected to an addition reaction.

  In the case of a polymer or copolymer of a monomer having the hydroxyl group or carboxyl group, the monomer having the epoxy group, the monomer having the aziridinyl group, or the monomer having the isocyanate group, An equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer can be subjected to an addition reaction. These reactions are preferably performed while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air.

  The amount of the radical polymerizable unsaturated group in the side chain of the acrylic resin (a-1) having a radical polymerizable unsaturated group in the side chain is the double bond equivalent (average per side chain radical polymerizable unsaturated group). The molecular weight is preferably from 1 to 3000 g / mol as calculated from the charged value from the viewpoint of improving scratch resistance and wear resistance. The double bond equivalent is more preferably 1 to 1200 g / mol, and still more preferably 1 to 800 g / mol. Thus, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking, the cured properties can be improved efficiently. In addition, the calculation method of a double bond equivalent is mentioned later.

  The number average molecular weight (Mn) of the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain is preferably 5,000 to 2,500,000, and 10,000 to 1,000,000. More preferably, it is 000. When Mn is 5,000 or more, when insert-molding the laminated sheet produced using the resin composition (A) containing the acrylic resin (a-1), the molding metal is used even if preheating is performed at the time of molding. The laminated sheet becomes difficult to stick to the mold. Moreover, the surface hardness of the laminated molded product to be manufactured is appropriate. On the other hand, when Mn is 2,500,000 or less, the synthesis is easy, and the appearance and adhesion with the acrylic resin base sheet (B) become good. A method for measuring Mn will be described later.

  The acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain preferably has a glass transition temperature (Tg) of 25 to 175 ° C, and more preferably 30 to 150 ° C. When Tg is 25 ° C. or higher, the mold peelability of the laminated sheet at the time of insert molding becomes good, and the surface hardness of the laminated molded product becomes appropriate. On the other hand, when Tg is 175 ° C. or lower, the handleability of the laminated sheet is improved. In consideration of the Tg of the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain, a vinyl polymerizable monomer having a high Tg when used as a homopolymer is used as the monomer. It is preferable. Further, from the viewpoint of improving weather resistance, it is more preferable to use (meth) acrylates as the main component as the vinyl polymerizable monomer. A method for measuring Tg will be described later.

  Further, as described later, when inorganic fine particles (a-3) are added to the resin composition (A), functional groups (hydroxyl groups, carboxyl groups, silanol groups, etc.) on the surface of the inorganic fine particles (a-3). ) Can be further improved in physical properties such as rigidity, toughness and heat resistance of the resin composition (A). Examples of the group capable of reacting with the functional group on the surface of the inorganic fine particles (a-3) include at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated silyl group, and an alkoxysilyl group. Can be mentioned. Examples of such a vinyl polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, vinyltrimethoxysilane, and γ- ( And (meth) acryloyloxypropyltrimethoxysilane. These may use only 1 type and can also use 2 or more types together.

[Photopolymerization initiator (a-2)]
When the resin composition (A) contains an acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain, the resin composition (A) contains a photopolymerization initiator (a-2). It is preferable to do. As a photoinitiator (a-2), the radical photopolymerization initiator which generate | occur | produces a radical by light irradiation, for example is mentioned.

  A known compound can be used as the radical photopolymerization initiator, and is not particularly limited. In consideration of yellowing during curing, deterioration during weathering, and the like, an initiator that does not contain an amino group in the molecule, such as an acetophenone series, a benzophenone series, or an acylphosphine oxide series, is preferable. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl A phosphine oxide is mentioned. These may use only 1 type and can also use 2 or more types together. For these compounds, it is preferable to use a compound having a boiling point that does not become a temperature higher than the boiling point during molding.

  Moreover, in order to raise the surface hardness of a molded article, you may add oxygen polymerization prohibition hardening inhibitors, such as n-methyldiethanolamine. Furthermore, in addition to these photopolymerization initiators, various peroxides may be added in consideration of curing using heat during molding. When the resin composition (A) contains a peroxide, the resin composition (A) needs to be cured at 150 ° C. for about 30 seconds. Therefore, peroxides having a low critical temperature, such as lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane and the like are preferably used. These may use only 1 type and can also use 2 or more types together.

  The addition amount of the photopolymerization initiator (a-2) is based on 100 parts by mass of the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain because the residual amount after curing affects the weather resistance. 0.1 to 5 parts by mass is preferable. In particular, when an amino radical photopolymerization initiator related to yellowing during curing is used as the photopolymerization initiator (a-2), the amount is preferably 1 part by mass or less.

[Inorganic fine particles (a-3)]
The resin composition (A) preferably further contains inorganic fine particles (a-3) from the viewpoint of improving scratch resistance and wear resistance. As the inorganic fine particles (a-3), as long as the transparency of the resin composition (A) is ensured, the type, particle diameter, and form thereof are not particularly limited. Examples of the inorganic fine particles (a-3) include colloidal silica, alumina, titanium oxide, tin oxide, foreign element doped tin oxide (ATO, etc.), indium oxide, foreign element doped indium oxide (ITO, etc.), cadmium oxide, and oxidation. Antimony etc. are mentioned. These may use only 1 type and can also use 2 or more types together. Among these, colloidal silica is preferable from the viewpoints of availability, price, transparency of the resin composition (A) layer, and expression of wear resistance.

  Colloidal silica can be used in the form of a normal aqueous dispersion or in a form dispersed in an organic solvent. However, in order to disperse uniformly and stably in the acrylic resin (a-1) having a radical polymerizable unsaturated group in the side chain, it is preferable to use colloidal silica dispersed in an organic solvent. Examples of the organic solvent include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like. These may use only 1 type and can also use 2 or more types together. Among these, from the viewpoint that it can be uniformly dispersed by the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain, the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain. It is preferable to select an organic solvent capable of dissolving

  Examples of colloidal silica dispersed in an organic solvent include commercially available products such as methanol silica sol MT-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG-ST, xylene / butanol. Silica sol XBA-ST, ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST Nissan Chemical Industries, Ltd.).

  The particle size of the inorganic fine particles (a-3) is preferably 200 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less, from the viewpoint of the transparency of the resin composition (A) layer. Moreover, as a lower limit of the particle diameter of inorganic fine particles (a-3), 1 nm or more is preferable. In addition, the particle diameter of the inorganic fine particles (a-3) is observed with a cross-sectional TEM photograph after the resin composition (A) layer containing the inorganic fine particles (a-3) is formed on the acrylic resin substrate sheet (B). To obtain the average value.

  The addition amount of the inorganic fine particles (a-3) is preferably 5 to 400 parts by mass in terms of solid content of the inorganic fine particles with respect to 100 parts by mass of the acrylic resin (a-1) having a radical polymerizable unsaturated group in the side chain. 10-200 mass parts is more preferable. When the addition amount of the inorganic fine particles (a-3) is 5 parts by mass or more, an effect of improving wear resistance is recognized. On the other hand, when the addition amount of the inorganic fine particles (a-3) is 400 parts by mass or less, the storage stability of the resin composition (A) is high and the moldability of the laminated sheet is also high.

  Moreover, as the inorganic fine particles (a-3), inorganic fine particles whose surface is previously treated with a silane compound represented by the following formula (I) may be used. This is because when the surface-treated inorganic fine particles are used, the storage stability of the resin composition (A) is further improved, and the surface hardness and weather resistance of the laminated sheet are also improved.

SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (I)
(In said formula (I), R < ⁴ > and R < ⁵ > represents the C1-C10 hydrocarbon group which may have an ether bond, an ester bond, an epoxy bond, or a carbon-carbon double bond, respectively. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond or a carbon-carbon double bond. 3 is an integer of 3, and c is an integer of 1 to 4 that satisfies 4-ab.

  Among the silane compounds represented by the formula (I), silane compounds represented by the following formulas (II) to (VII) are more preferable.

SiR ⁷ _a R ⁸ _b (OR ⁹ ) _c (II)
SiR ⁷ _n (OCH ₂ CH ₂ OCO (R ¹⁰ ) C═CH ₂ ) _4-n (III)
CH ₂ ═C (R ¹⁰ ) COO (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (IV)
CH ₂ = CHSiR ¹¹ _n (OR ⁹ ) _3-n (V)
HS (CH ₂ ) _p SiR ¹¹ _n (OR ⁹ ) _3-n (VI)

(In the formulas (II) to (VII), R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond. R ⁹ Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and a and b are respectively C is an integer of 1 to 4 that satisfies 4-ab, n is an integer of 0 to 2, and p is an integer of 1 to 6.)

  Examples of the silane compound represented by the formula (II) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyl Dimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxypropi Trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the formula (III) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane. It is done.

  Examples of the silane compound represented by the formula (IV) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxyethyldimethoxymethyl. Examples thereof include silane and γ-methacryloyloxypropyltrimethoxysilane.

  Examples of the silane compound represented by the formula (V) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  Examples of the silane compound represented by the formula (VI) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the formula (VII) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane. These silane compounds may be used alone or in combination of two or more.

  A method for adding the inorganic fine particles (a-3) to the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain is not particularly limited. For example, after synthesizing an acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain in advance, the inorganic fine particles (a-3) may be mixed, or the radically polymerizable unsaturated group in the side chain. Arbitrary methods, such as a method of polymerizing the monomer, can be selected under a condition in which the monomer constituting the acrylic resin (a-1) having a mixture of inorganic fine particles (a-3) is mixed. .

[Light stabilizer (a-4)]
It is preferable from a viewpoint of a weather resistance improvement that a resin composition (A) contains a light stabilizer (a-4) further. A known light stabilizer can be used as the light stabilizer (a-4), and is not particularly limited. However, it is preferable to use a hindered amine light stabilizer among the light stabilizers.

  The hindered amine light stabilizer is a compound having a piperidine ring in which a plurality of substituents having a steric hindrance action are bonded to two adjacent carbon atoms of a nitrogen atom. Examples of the substituent having such steric hindrance include a methyl group. Preferred examples of the compound having such a substituent include a 2,2,6,6-tetramethyl-4-piperidyl group such as bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate. And a compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group. Commercially available products include, for example, Chimassorb 119FL, 2020FDL, 944FD, 944LD, Tinuvin 622LD, 123S, 144, 765, 770, 770DF, 770FL, 111FD, 123, 292 (trade names, manufactured by Ciba Specialty Chemicals Co., Ltd.) ), Sanol LS-770, LS-765, LS-292, LS-2626, LS-744, LS-440 (trade name, manufactured by Sankyo Co., Ltd.), ADK STAB LA-57, LA-62, LA-63 , LA-68 (trade name, manufactured by ADEKA Corporation) and the like. These hindered amine light stabilizers may be used alone or in combination of two or more. However, when inorganic fine particles (a-3) are contained in the resin composition (A), if a hindered amine light stabilizer in which the substituent on the nitrogen atom in the piperidine ring is a hydrogen atom is used, the inorganic fine particles (a -3) aggregation may occur, and the storage stability of the resin composition (A) may decrease, or the transparency and wear resistance of the resin composition (A) layer may decrease. When used in combination with the inorganic fine particles (a-3), it is preferable to use a hindered amine light stabilizer in which the substituent on the nitrogen atom is an alkyl group such as a methyl group or an alkoxy group such as an octyloxy group.

  The content of the light stabilizer (a-4) is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain. 1-10 mass parts is more preferable, and 0.2-5 mass parts is still more preferable. When content of a light stabilizer (a-4) is 0.1-15 mass parts, a weather resistance improves and it has high economical efficiency. Further, the laminated sheet roll is not easily soiled by the light stabilizer (a-4) bleed and the appearance of the laminated sheet is not deteriorated, and the surface hardness of the laminated molded product obtained by laminating the laminated sheets is improved.

[Solvent (S)]
Although a solvent (S) is not specifically limited, each component of a resin composition (A) is melt | dissolved or disperse | distributed uniformly, and the physical property (mechanical strength, transparency, etc.) of an acrylic resin base material sheet (B) A solvent that does not substantially cause a decrease in the above is preferred. Moreover, the volatile solvent which has a boiling point lower than Tg + 80 degreeC of the resin component which is a main structural component of an acrylic resin base sheet (B), Preferably a lower boiling point than Tg + 30 degreeC is preferable.

  Examples of such solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and ethylene glycol, aromatic solvents such as xylene, toluene, and benzene, and aliphatic hydrocarbons such as hexane and pentane. Solvents, halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride, phenol solvents such as phenol and cresol, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, diethyl ether, methoxytoluene, 1,2-dimethoxyethane Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, tetrahydrofuran (THF), and fatty acid solvents such as formic acid, acetic acid, propionic acid , Acid anhydrides such as acetic anhydride Agent, ester solvents such as ethyl acetate, butyl acetate, butyl formate, nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide, dimethylacetamide, sulfur-containing solvents such as thiophene, dimethyl sulfoxide, diacetone alcohol, 2-methoxyethanol (Methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, a solvent having two or more functional groups such as morpholine, or water These various known solvents can be used.

  Moreover, it is preferable that the mass ratio of the resin composition (A) / solvent (S) in the mixed solution is 25/75 to 70/30 (total 100 parts by mass). If the resin composition (A) is 25 parts by mass or more, a large amount of the solvent (S) does not remain in the laminated sheet, and the surface of the resin composition (A) layer does not have adhesiveness. Become. Further, it does not cause a decrease in yield in the printing process, a decrease in storage stability in a roll state, or a decrease in mold contamination during insert molding. On the other hand, if the resin composition (A) is 70 parts by mass or less, the viscosity is not high, and the appearance of the laminated sheet is not deteriorated.

[Acrylic resin base sheet (B)]
In the present invention, the acrylic resin base sheet (B) is used from the viewpoint of weather resistance, transparency and the like. The acrylic resin base sheet (B) is preferably a thermoplastic resin base sheet having a crosslinked rubber component.

(Tensile modulus)
As the acrylic resin base sheet (B) of the present invention, the acrylic resin base sheet (B) having an elongation of 100% or more when heated at 100 ° C. is formed into a mold shape during insert molding or in-mold molding. This is preferable because the followability becomes good.

  From the viewpoint of the hardness of the finally obtained laminated molded article and the scratch resistance in the process of producing the laminated molded article, the thermoplastic acrylic resin substrate sheet of the present invention has a tensile modulus of 1 under the condition of 23 ° C. 500 MPa or more and 3,500 MPa or less are preferable.

(Pencil hardness)
The pencil hardness (measurement based on JIS K5400) of the acrylic resin base sheet (B) of the present invention is not particularly limited, but is preferably 2B or more from the viewpoint of the hardness of the finally obtained laminated molded product. , HB or more is preferable, and F or more is particularly preferable.

(thickness)
Although the thickness of the acrylic resin base material sheet (B) of this invention is not specifically limited, 10-500 micrometers is preferable. By setting the thickness of the acrylic resin base sheet (B) to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and a film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin substrate sheet (B) 10 μm or more, a sense of depth can be more sufficiently imparted to the resulting laminate together with the protection of the substrate. As for the thickness of an acrylic resin base material sheet (B), 30-300 micrometers is more preferable, and 50-200 micrometers is especially preferable.

  The acrylic resin base sheet (B) is obtained by dispersing 3 to 50% by mass of an acrylic crosslinked rubber in 95 to 50% by weight of an acrylic resin having methyl methacrylate as a main component and a glass transition temperature of 40 to 105 ° C. Is preferred. Examples of the acrylic crosslinked rubber include a polymer obtained by graft polymerization of a monomer mainly containing methyl methacrylate in the presence of a rubber having at least one selected from n-butyl acrylate and 2-ethylhexyl acrylate as a main constituent unit. It is done.

  Examples of the thermoplastic acrylic resin base sheet as described above are disclosed in, for example, JP-A-8-323934, JP-A-9-263614, JP-A-11-147237, JP-A-2001-1067. The transparent thermoplastic acrylic sheet currently used is mentioned. Examples of commercially available thermoplastic acrylic resin base sheets having a crosslinked rubber component include acryloprene HBX-N47, HBS-006, HBD-013, HBS-010, HBA-001, and HBA-002 (trade names, Mitsubishi Rayon Co., Ltd.), Technoloy S001, S003, SN101 (above trade name, manufactured by Sumitomo Chemical Co., Ltd.), Sandulen SD007, SD009 (above trade name, manufactured by Kaneka Corporation).

  In the acrylic resin base sheet (B), if necessary, lubricants such as polyethylene wax and paraffin wax, lubricants such as silica, spherical alumina and scaly alumina, benzotriazole, benzophenone, salicylic acid ester, etc. Organic UV absorbers, inorganic UV absorbers such as zinc oxide, cerium oxide, titanium oxide, light stabilizers such as hindered amine radical scavengers, piperidine radical scavengers, plasticizers, stabilizers, pigments, Various additives such as dyes may be added as appropriate.

[Corona discharge]
When applying the mixed solution on the acrylic resin base sheet (B), in order to improve the adhesion between the acrylic resin base sheet (B) and the resin composition (A) layer, It is preferable to activate the surface of the acrylic resin substrate sheet (B). Immediately after being activated by the corona discharge, the adhesiveness is the highest, so the corona discharge is preferably performed immediately before the application of the mixed solution. Furthermore, when the resin composition (A) is a photocurable resin composition, acrylic is used for the purpose of preventing volume shrinkage at the time of photocuring and lowering the adhesion with the acrylic resin substrate sheet (B). It is preferable to previously laminate a primer layer on the resin base sheet (B).

<Heat drying process>
The solvent (S) is volatilized by heating and drying the acrylic resin base sheet (B) coated with the mixed solution, thereby forming a resin composition (A) layer on the acrylic resin base sheet (B). A known method can be used as the heat drying method. Examples thereof include heat drying such as hot air drying and hot roll drying, infrared drying, and the like, and can be appropriately selected.

[Elongation rate (L)]
When an external force (f) (N) is applied to the acrylic resin base sheet (B) during heat drying, an internal force (f) (N) equal to the external force is applied to the inside of the acrylic resin base sheet (B). Acts to generate stress. The internal force (f) per unit area is called normal stress (σ) (N / mm ² ) and is calculated by the following equation (2).

σ = f / A (2)
Here, A is a cross-sectional area (mm ² ) of the acrylic resin base sheet (B), and is obtained from the product of the thickness (t) (mm) and the width (W) (mm) of the acrylic resin base sheet (B). Desired. The normal stress (σ) is positive when the acrylic resin base sheet (B) is stretched (tensile stress) and negative when the acrylic resin base sheet (B) is contracted (compressive stress). It is defined as When tension (F1) (N) is applied in the flow direction (MD direction) of the acrylic resin substrate sheet (B) during drying by heating, the length of the acrylic resin substrate sheet (B) is reduced from L ₀ (mm) to L Suppose that it changed to ₁ (mm). The normal stress (σ) (N / mm ² ) and elongation (L) (%) at this time are expressed by the following formulas (3) and (4), respectively.

  There is a material-specific relationship between normal stress (σ) and elongation (L), and in a small range of elongation (L), there is a proportional relationship between normal stress (σ) and elongation (L). And the following equation (5) is established.

σ = E * L / 100 (5)
Here, E is the tensile elastic modulus (MPa) in the flow direction of the acrylic resin base sheet (B) during heat drying. The formula (1) can be obtained from the formula (3) and the formula (5).

  The elongation rate (L) of the acrylic resin base sheet (B) during heat drying represented by the formula (1) needs to be 0.001% or more and 0.5% or less. The value of the elongation (L) is preferably 0.003% or more and 0.45% or less, and more preferably 0.005% or more and 0.4% or less. When the elongation (L) is less than 0.001%, the acrylic resin base sheet (B) needs to be loosened and conveyed. On the other hand, when it exceeds 0.5%, the acrylic resin substrate sheet (B) is deformed to cause wrinkles and sagging and unevenness occurs on the surface. In addition, the measuring method of the tension | tensile_strength (E1) concerning the tension | tensile_strength (F1) concerning the acrylic resin base material sheet (B) at the time of heat drying and the flow direction of the acrylic resin base material sheet (B) at the time of heat drying is mentioned later.

[Heating temperature]
About the heating temperature in heat drying, it is necessary to fully investigate from a viewpoint of the value of elongation rate (L), and the residual | survival of a solvent (S). If the heating temperature is too high, the tensile elastic modulus (E) in the flow direction of the acrylic resin base sheet (B) during heat drying may decrease, leading to an increase in elongation (L). On the other hand, when the heating temperature is too low, a large amount of the solvent (S) remains in the laminated sheet, and the surface of the resin composition (A) layer may become sticky. As long as the heating temperature is such that the elongation (L) value is 0.001% or more and 0.5% or less and the solvent (S) is sufficiently volatilized, the acrylic resin base sheet (B) to be used is used. And the solvent (S) can be selected as appropriate.

<Winding process>
A laminated sheet roll including the resin composition (A) layer and the acrylic resin base sheet (B) formed by the above process is wound to produce a laminated sheet roll. As a method for winding the laminated sheet, a known method can be used. For example, a near winding method in which a roller is brought into close contact without contact, a touch winding method in which a touch roller is completely brought into contact with a laminated sheet, and the like can be mentioned. Further, when winding, a taper can be provided to lower the final winding tension with respect to the initial winding tension (taper winding). In taper winding, the ratio of the final winding tension to the initial winding tension (taper rate) can be set to an arbitrary value depending on the acrylic resin substrate sheet (B) to be used and the winding conditions.

[Tension per unit width (F2)]
The tension (F2) per unit width of the laminated sheet (hereinafter also referred to as tension (F2) per unit width) at the time of winding the laminated sheet needs to be 60 N / m or more and 170 N / m or less. The value of tension (F2) per unit width is preferably 65 N / m or more and 165 N / m or less, and more preferably 70 N / m or more and 160 N / m or less. When the tension (F2) per unit width is less than 60 N / m, winding collapse occurs, and the winding shape of the laminated sheet roll becomes defective. On the other hand, when it exceeds 170 N / m, appearance defects such as gauge bands, wrinkles and sagging occur in the laminated sheet roll. A method for measuring the tension (F2) per unit width will be described later. Further, in the case of taper winding, it is preferable that all the tensions (F2) per unit width that fluctuate fall within the above range.

[Middle layer]
The laminated sheet according to the present invention has a structure in which the resin composition (A) layer is laminated on the acrylic resin base sheet (B), and has excellent physical properties such as insert molding and in-mold molding, as well as various physical properties. In particular, it is possible to give a laminated molded article having excellent weather resistance-abrasion resistance (surface hardness) -adhesion balance. Between the resin composition (A) layer and the acrylic resin base sheet (B), an intermediate layer composed of one or more resin compositions is further laminated as long as the excellent properties of the laminated sheet are not impaired. You can also At this time, as the resin composition of the intermediate layer, it is possible to use a resin composition equivalent or similar to the resin composition (A), so that the surface properties of the laminated sheet (particularly adhesion, weather resistance, appearance, design properties) Etc.) are preferred because they tend to be good.

[Protective film (C)]
In the laminated sheet according to the present invention, the protective film (C) can be laminated on the resin composition (A) layer on the acrylic resin substrate sheet (B). The protective film (C) is effective for preventing dust on the surface of the resin composition (A) layer, and also effective for preventing scratches on the surface of the resin composition (A) layer.

  The protective film (C) is in intimate contact with the resin composition (A) layer, and is formed in a state of being peeled or bonded before molding, and then peeled off. And good releasability. Any protective film that satisfies such conditions can be selected and used. Examples of such a protective film include a polyethylene film, a polypropylene film, and a polyester film.

  Lamination | stacking of a protective film (C) can be performed before the process of winding up a lamination sheet. When laminating the protective film (C), the temperature of the laminated sheet is preferably 10 ° C. or higher and 33 ° C. or lower, and more preferably 15 ° C. or higher and 33 ° C. or lower. If the temperature of a laminated sheet is 10 degreeC or more, a protective film (C) can be bonded together without generating dew condensation on a laminated sheet. Moreover, if it is 33 degrees C or less, the deformation | transformation of the lamination sheet of the lamination sheet roll after winding can be suppressed, and the lamination sheet unwound from the lamination sheet roll becomes favorable appearance.

[Decoration layer]
In the laminated sheet unwound from the laminated sheet roll produced by the method according to the present invention, at least one decorative layer selected from a printing layer and a vapor deposition layer is laminated on the acrylic resin base sheet (B) side surface. It can be set as a laminated sheet for molding. The decorative layer is used to decorate the surface of the molded product with patterns, characters, and the like. Although the form of decoration is arbitrary, for example, a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full-color solid, etc. may be mentioned. Moreover, the laminated sheet for molding may further have an adhesive layer laminated on the decorative layer.

[Print layer]
Materials for the printing layer include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose It is preferable to use an ink containing an appropriate color pigment or dye as a colorant using a resin such as an ester resin, an alkyd resin, or a chlorinated polyolefin resin as a binder.

  As the ink pigment, for example, the following can be used. As yellow pigments, azo pigments such as polyazo, organic pigments such as isoindolinone, inorganic pigments such as chrome lead, azo pigments such as polyazo as red pigments, organic pigments such as quinacridone and inorganic pigments such as petals, An organic pigment such as phthalocyanine blue or an inorganic pigment such as cobalt blue can be used as the blue pigment, an organic pigment such as aniline black as the black pigment, and an inorganic pigment such as titanium dioxide as the white pigment. As the ink dye, various known dyes can be used as long as the effects of the present invention are not impaired.

  As the ink printing method, it is preferable to use a known printing method such as an offset printing method, a gravure rotary printing method or a screen printing method, or a known coating method such as a roll coating method or a spray coating method.

[Deposition layer]
As a material of the vapor deposition layer, at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, or an alloy or compound thereof is used. Can be used. The vapor deposition layer can be formed by a method such as vacuum vapor deposition, sputtering, ion plating, or plating. The thickness of the printing layer or the vapor deposition layer for decorating can be appropriately selected according to the degree of expansion during molding so that the desired surface appearance of the laminated molded product can be obtained.

[Adhesive layer]
As the material for the adhesive layer, any synthetic resin material can be selected and used as long as it has the property of improving the adhesion between the printed layer or vapor deposition layer and the molding resin. For example, when the molding resin is a polyacrylic resin, it is preferable to use a polyacrylic resin as a material. Also, when the molding resin is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide resin that has an affinity for these resins It is preferable to use a resin or the like as a material. Furthermore, when the molding resin is a polyolefin resin such as a polypropylene resin, heat using chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, or blocked isocyanate A curable urethane resin or the like can be used as a material. In addition, hydrophobic silica, an epoxy resin, a petroleum resin, or the like can be further included for the purpose of reducing the tackiness of the adhesive layer or improving the heat resistance.

[Laminated sheet for molding]
The thickness of the molding laminated sheet according to the present invention is preferably 0.030 to 0.750 mm. If the thickness of the forming laminated sheet is 0.030 mm or more, deep drawing can be performed without significantly reducing the thickness of the forming laminated sheet on the curved surface. Moreover, if the thickness of the shaping | molding laminated sheet is 0.750 mm or less, the shaping | molding lamination sheet can be shape | molded, without reducing the shape followability to the metal mold | die of the shaping | molding lamination sheet.

[Laminated molded products]
The laminated molded product according to the present invention is a laminated sheet unwound from the laminated sheet roll or the laminated sheet for molding (hereinafter also simply referred to as a sheet) so that the resin composition (A) layer becomes the outermost surface layer. Is a laminated molded product in which is laminated. By laminating so that the resin composition (A) layer is on the surface, the surface properties (such as weather resistance, appearance, and design properties) of the resin composition (A) layer can be imparted to the laminated molded product. When the protective film (C) is laminated on the sheet, the protective film (C) is usually peeled off just before laminating the sheet on the surface of the molded product. You may affix a sheet | seat on the molded article surface so that it may become a surface layer.

  A known production method can be used as a method for producing the laminated molded product, and is not particularly limited. Examples thereof include an insert molding method, an in-mold molding method, and a method using a vacuum molding machine disclosed in JP-A-2002-67137.

  With the insert molding method, a sheet is formed into a three-dimensional shape by vacuum forming or the like in advance, an unnecessary sheet portion is removed, then transferred into an injection mold, and a molding resin as a base material is injection molded. It is a method of producing a laminated molded product by integrating them.

  With the in-mold molding method, a sheet is placed in an injection mold, subjected to vacuum molding, and then molded into a base material in the same mold by injection molding to produce a laminated molded product. It is a method to do.

  In the method using a vacuum forming machine disclosed in Japanese Patent Application Laid-Open No. 2002-67137, first, two sealed spaces partitioned by a sheet are formed, and a molded body is arranged on one space side. The pressure is reduced. Thereafter, the sheet is heated and softened, and only the other space where the molded body is not disposed is returned to normal pressure in a state where the molded body is pressed against the sheet surface from one space side toward the other space side. Thereby, it is the method of sticking a sheet | seat on a molded object using differential pressure | voltage. Moreover, the method of decompressing only the space which has arrange | positioned the molded object may be used. According to this method, since the heated sheet is uniformly and pressure-applied to the surface of the molded body, the sheet is satisfactorily adhered to the molded body even if the surface of the molded body is a curved surface or the like. Can do. As an apparatus for performing such a molding process, for example, a TOM (Three Dimension Overlay Method) molding machine (manufactured by Fuse Vacuum Co., Ltd.) can be exemplified.

  As the molding resin, any resin capable of various molding such as injection molding can be used, and there is no particular limitation. Examples of the molding resin include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymer resins, and olefin thermoplastic elastomers. Olefin resin, polystyrene resin, ABS resin (acrylonitrile / butadiene / styrene copolymer), AS resin (acrylonitrile / styrene copolymer), acrylic resin, urethane resin, unsaturated polyester resin, General-purpose thermoplastic resins such as epoxy resins or thermosetting resins, polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, polycarbonate-modified polyphenylene ether resins, polyethylene terephthalate resins, etc. General purpose engineering resins, and polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resin, polyetherimide resin, polyimide resin, liquid crystal polyester resins and super engineering resins such as polyallyl heat-resistant resin. These may use only 1 type and may use 2 or more types together.

  Depending on the purpose, the molding resin may contain glass fibers, talc, calcium carbonate, silica, reinforcing materials such as inorganic fillers such as mica, composite resins added with modifiers such as rubber components, and various modified resins. Can do. Furthermore, it is preferable that the shrinkage rate after molding of the molding resin is approximated to the shrinkage rate of the laminated sheet, so that problems such as warpage of the laminated molded product and peeling of the sheet tend to be eliminated.

  The laminated sheet or the laminated sheet for molding according to the present invention can be used by laminating directly or via an adhesive layer on an article already molded by injection molding or the like and laminating it on the surface of the molded product.

  Unnecessary portions of the sheet formed at the end of the laminated molded product can be appropriately trimmed and removed. The trimming time may be any time after the sheet is inserted and placed in the mold and after the laminated molded product is taken out. As a method of trimming unnecessary portions, for example, a method of burning a sheet by irradiating a laser beam or the like, a method of producing a punching die for trimming, a method of punching a sheet by pressing, and a method of removing the sheet by tearing manually Is mentioned.

  According to the method of the present invention, it is possible to improve appearance defects such as gauge bands, wrinkles, sagging, and collapse of the laminated sheet roll, and the unrolled laminated sheet has excellent appearance, design properties, and wear resistance. , Chemical resistance and weather resistance. The laminated sheet is used for automotive interior materials such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, weather strips, bumpers, bumper guards, side mud guards, body panels. , Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, etc. Applications for front panels, buttons, emblems, surface cosmetics, etc. for home appliances, applications for housings for mobile phones, display windows, buttons, etc., and for furniture exterior materials Building interior materials such as walls, ceilings and floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates and windbreak boards, surfaces of furniture such as window frames, doors, handrails, sills, and duck Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior materials, bottles, cosmetic containers, small items, etc. It can be suitably used for various other uses such as packaging containers and materials, miscellaneous goods such as prizes and accessories. Further, the transparent resin can be suitably used for windows, headlamp covers, windshield parts and the like of automobiles, railway vehicles, airplanes, etc. while making use of the transparency. In addition, the number of processes can be omitted as compared with the case where the surface of the molded product is painted, and the productivity is high and the burden on the environment is small.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. “Part” means “part by mass”. In addition, various measurements and evaluations in this example were performed by the following methods.

(1) Polymerization rate The polymerization rate of the monomer in the acrylic resin I was measured by the following method. The monomer remaining in the solution of the acrylic resin I obtained by polymerization was analyzed by gas chromatography (manufactured by Agilent Technologies, trade name: HP6890), and the polymerization rate (%) was determined from the amount of the remaining monomer. Was calculated.

(2) Solid content The solid content of the acrylic resin I was measured by the following method. About 1 g of a solution or dispersion of acrylic resin I is collected on an aluminum dish, and after the solvent or dispersion medium is volatilized at room temperature, the mass of the transparent solid of acrylic resin I obtained by heating at 80 ° C. for 1 hour Was measured, and the solid content (mass%) was calculated.

(3) Number average molecular weight (Mn)
Mn of the acrylic resin I was measured using a high-speed GPC device (trade name: HLC-8220GPC, manufactured by Tosoh Corporation). In addition, about the numerical value, the value converted into polystyrene was used.

(4) Double bond equivalent The double bond equivalent of the acrylic resin I is the double bond equivalent by estimating the structure of the acrylic resin I obtained from the prescription of synthesis and the polymerization rate of the monomer calculated by the method described above. (G / mol) was calculated.

(5) Glass transition temperature (Tg)
The Tg (° C.) of the acrylic resin I was measured using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.).

(6) Unwinding The deviation of the end face of the laminated sheet roll after winding up the laminated sheet was visually evaluated according to the following criteria.

○: There is almost no deviation of the end face of the laminated sheet roll (a usable state).
X: There is a shift of the end face of the laminated sheet roll (unusable state).

(7) Surface irregularities The deformation (gauge band, wrinkle, sagging) of the laminated sheet when the rolled-up laminated sheet roll was unwound again with a tension of 100 N / m was visually evaluated according to the following criteria.

○: No deformation ×: Deformation

(8) Tensile modulus (E) in the flow direction of the acrylic resin base sheet (B) during heat drying
In accordance with JIS K6251, five test pieces of the acrylic resin base sheet (B) were prepared using a super dumbbell cutter (manufactured by Dumbbell Co., Ltd., trade name: SDK-100D). About the obtained test piece, Strograph T (Corporation | KK Toyo Seiki Seisakusho make, brand name) was used, and the tensile elasticity modulus (E) was measured. Before fixing the test piece to the apparatus, the inside of the apparatus is set to the same temperature as in the hot-air dryer during heat drying, and after confirming that the set temperature has been reached, the test piece is fixed in the apparatus. It was left in the apparatus for a minute. Then, the tensile test of each test piece was implemented with the tensile speed of 500 mm / min, the average value of the tangent of the stress strain curve at that time was calculated | required, and it was set as the tensile elasticity modulus (E) (MPa).

(9) Tension (F2) per unit width of the laminated sheet at the time of winding the laminated sheet
The tension (F2) (N / m) per unit width applied to the laminated sheet displayed on the control monitor of the coating machine (Hirano Tech Seed gravure coater) was read.

(10) Tension (F1) applied to the acrylic resin substrate sheet (B) during drying by heating
The tension (N / m) per unit width and the width (m) of the acrylic resin substrate sheet (B) applied to the acrylic resin substrate sheet (B) during heating and drying, which are displayed on the control monitor of the coating machine. From the above, the tension (F1) (N) applied to the acrylic resin substrate sheet (B) during heat drying was calculated.

[Example 1]
(Synthesis of acrylic resin I)
50 parts of methyl ethyl ketone was put into a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 80 parts of methyl methacrylate, 20 parts of glycidyl methacrylate and 0.5 part of azobisisobutyronitrile was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of methyl ethyl ketone and 0.2 part of azobisisobutyronitrile was added and polymerized. After 4 hours, 50 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added and stirred at 80 ° C. for 30 hours while blowing air. Thereafter, the reaction mixture was cooled and the reaction product was taken out from the flask to obtain a solution of acrylic resin I having a radical polymerizable unsaturated group in the side chain. The polymerization rate of the monomer in the acrylic resin I is 99.5% or more, the solid content of the acrylic resin I is about 40% by mass, the Mn is about 60,000, the double bond equivalent is 614 g / mol, and the Tg is 88 ° C. Met.

(Synthesis of colloidal silica S1)
The components listed in Table 1 were placed in a flask equipped with a stirrer, a condenser and a thermometer, and the temperature of the hot water bath was 75 ° C. while stirring. By reacting at 75 ° C. for 2 hours, colloidal silica S1 whose surface was treated with a silane compound and dispersed in methanol was obtained. Subsequently, the operation of adding toluene after distilling off methanol was repeated, and methanol was completely replaced with toluene. Thereby, the surface was processed with the silane compound, and colloidal silica S1 dispersed in toluene was obtained.

Note) Numerical values in Table 1 indicate parts by mass. (As for MT-ST, the mass part in terms of solid content is shown)
1) MT-ST: Methanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name, silica particle diameter 15 nm)
2) KBM503: γ-methacryloyloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

(Preparation of mixed solution)
Using the synthesized acrylic resin I and colloidal silica S1, a mixed solution containing a resin composition (A) having the composition shown in Table 2 and a solvent (S) (MEK: toluene = 4: 1) was prepared.

Note) Numerical values in the resin composition (A) are parts by mass. (In terms of acrylic resin I and colloidal silica S1, solid parts are expressed in mass parts.)
1) Photopolymerization initiator: Irg184 [1-hydroxycyclohexyl phenyl ketone (trade name, manufactured by Ciba Specialty Chemicals)]
2) Light stabilizer: Tinuvin 123 [decanedioic acid bis (2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (Product name, manufactured by Ciba Specialty Chemicals)
3) MEK: methyl ethyl ketone.

(Manufacture of laminated sheet rolls)
The prepared mixed solution is placed on one side of an acrylic resin base sheet (B) (trade name: HBS-010P, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness (t) of 0.075 mm and a base width (W) of 1100 mm. The reverse gravure method was applied with a coating width of about 1100 mm. Subsequently, a tension (F1) of 130 N is applied to the acrylic resin base sheet (B), and the acrylic resin base sheet (B) is conveyed in the flow direction of the acrylic resin base sheet (B) at a speed of 20 m / min. And dried at 70 ° C. for about 40 seconds. As a result, the solvent (S) was sufficiently volatilized to form a resin composition (A) layer having a thickness of about 0.008 mm to obtain a laminated sheet. Further, a protective film (C) having a thickness of 0.060 mm and a base material width of 1095 mm (manufactured by Sanei Kaken Co., Ltd., trade name: Sanitect PAC-3-60) was attached to the surface of the resin composition (A) layer. . The temperature of the laminated sheet at this time was 30 ° C. Thereafter, a tension of 100 N / m per unit width of the laminated sheet (F2, taper ratio: 5% (final tension is adjusted to 95 N / m)) is applied to the laminated sheet, and the laminated sheet 500 m is wound up by the near winding method. It was. Thereby, the lamination sheet roll was manufactured. The laminated sheet roll did not collapse, and surface irregularities were not confirmed on the unrolled laminated sheet. Moreover, the tensile elasticity modulus (E) of the flow direction of the acrylic resin base sheet (B) at 70 ° C. was 1050 MPa. The results are shown in Table 3.

[Comparative Example 1]
A laminated sheet roll was produced in the same manner as in Example 1 except that the tension (F2) per unit width of the laminated sheet at the time of winding the laminated sheet was 50 N / m (taper rate: 5%). However, the occurrence of collapse was confirmed during winding. Since the tension at the time of winding was too low, it is considered that the end portion was displaced due to the collapse of winding. The results are shown in Table 3.

[Comparative Example 2]
Example 1 except that the tension (F2) per unit width of the laminated sheet at the time of winding the laminated sheet was 180 N / m (taper rate: 5%), and the temperature of the hot air dryer in heat drying was 80 ° C. A laminated sheet roll was produced in the same manner as described above. The tensile elastic modulus (E) in the flow direction of the acrylic resin base sheet (B) at 80 ° C. was 720 MPa, and the temperature of the laminated sheet when the protective film (C) was bonded was 26 ° C. Unevenness of the surface was confirmed on the unrolled laminated sheet. It is considered that since the tension at the time of winding was too high, the gauge band became prominent and irregularities were generated on the surface of the laminated sheet. The results are shown in Table 3.

[Comparative Example 3]
Example, except that the tension (F2) per unit width of the laminated sheet at the time of winding the laminated sheet was 150 N / m (taper rate: 5%), and the temperature of the hot-air dryer at the time of heat drying was 100 ° C. A laminated sheet roll was prepared in the same manner as in 1. The tensile elastic modulus (E) in the flow direction of the acrylic resin base sheet (B) at 100 ° C. was 300 MPa. Since the elongation (L) was too large, wrinkles and sagging were generated due to the deformation of the unrolled laminated sheet, irregularities were generated on the surface, and the appearance was poor. The results are shown in Table 3.

[Example 2]
The protective film (C) of the laminated sheet unwound from the laminated sheet roll obtained in Example 1 was peeled in advance, and then placed in the mold. At this time, it arrange | positioned so that the resin composition (A) layer side surface of a lamination sheet might face the inner wall face of a metal mold | die. Next, the laminated sheet was preheated at 350 ° C. for 10 seconds using an infrared heater. Then, the laminated sheet was made to follow the shape of the mold by vacuum suction while heating. The shape of the mold was a truncated pyramid shape. The size of the truncated surface was 100 mm × 100 mm, the size of the bottom surface was 108 mm × 117 mm, the depth was 10 mm, and the radii of curvature at the ends of the truncated surface were 3, 5, 7, and 10 mm, respectively. When the mold following ability was visually evaluated, each end portion followed well. Next, in-mold molding was performed using a polycarbonate resin as a molding resin under conditions of a molding temperature of 280 to 300 ° C. and a mold temperature of 40 to 60 ° C. Thus, a molded product in which the laminated sheet was in close contact with the surface of the molded product was obtained. No defects were found in the appearance of the molded product. Next, the resin composition (A) layer was cured by irradiating the molded product with ultraviolet rays of about 600 mJ / cm ² using an ultraviolet irradiation device. As a result, a laminated molded article having high surface hardness and high wear resistance, and excellent gloss and design was obtained.

[Comparative Examples 4 and 5]
A laminated molded product was produced in the same manner as in Example 2 except that the laminated sheet unwound from the laminated sheet roll obtained in Comparative Examples 2 and 3 was used. Since a laminated sheet with surface irregularities was used, defects resulting from surface irregularities occurred in the obtained laminated molded product.

[Example 3]
Gravure printing the pattern on the acrylic resin base sheet (B) side surface of the laminated sheet unrolled from the laminated sheet roll obtained in Example 1 using inks of black, brown and yellow pigments. Printed by law. As a result, a printing layer was formed to obtain a laminated sheet for molding. Since the laminated sheet had no surface tackiness, printability was good. When the laminated sheet for printing after printing was visually observed to evaluate the presence or absence of printing omission, no printing omission was observed.

[Comparative Examples 6 and 7]
A laminated sheet for molding was produced in the same manner as in Example 3, except that the laminated sheet unwound from the laminated sheet roll obtained in Comparative Examples 2 and 3 was used. Since the laminated sheet had no surface tackiness, printing was possible. However, since the surface unevenness was generated in the laminated sheet, printing omission due to the surface unevenness was observed in the molded laminated sheet after printing, and the printability was low.

[Example 4]
The molding laminated sheet obtained in Example 3 was placed in a mold. At this time, after the protective film (C) of the laminated sheet for molding was peeled in advance, the resin composition (A) layer side surface of the laminated sheet was disposed so as to face the inner wall surface of the mold. Next, the laminated sheet for molding was preheated at 300 ° C. for 15 seconds using an infrared heater. Thereafter, the laminated sheet for molding was made to follow the shape of the mold by vacuum suction while heating. The mold followability of the molding laminated sheet was good. The same mold as that used in Example 2 was used as the mold. Next, in-mold molding was performed using acrylonitrile / butadiene / styrene copolymer resin as a molding resin under conditions of a molding temperature of 220 to 250 ° C. and a mold temperature of 40 to 60 ° C. As a result, a molded product having the molded laminated sheet adhered to the surface of the molded product was obtained. The mold releasability of the molding laminated sheet was good. The molded article had no printing omission and good appearance. Next, the resin composition (A) layer was cured by irradiating the molded product with ultraviolet rays of about 600 mJ / cm ² using an ultraviolet irradiation device. As a result, a laminated molded article having high surface hardness and abrasion resistance, excellent gloss, a printed pattern, and excellent design properties was obtained.

[Comparative Examples 8 and 9]
A laminated molded product was produced in the same manner as in Example 4 except that the molded laminated sheets obtained in Comparative Examples 6 and 7 were used. Although the laminated molded product had high surface hardness and abrasion resistance, printing omission due to surface irregularities was observed, and the laminated molded product was inferior in design.

[Example 5]
On the printing layer of the molding laminated sheet obtained in Example 3, an adhesive layer made of chlorinated polypropylene resin (chlorination degree: 15%) was formed by a gravure printing method. The molding laminated sheet was placed in a mold. At this time, after the protective film (C) of the laminated sheet for molding was peeled in advance, the resin composition (A) layer side surface of the laminated sheet was arranged so as to face the inner wall surface of the mold. Next, the laminated sheet for molding was preheated at 300 ° C. for 15 seconds using an infrared heater. Thereafter, the laminated sheet for molding was made to follow the shape of the mold by vacuum suction while heating. The mold followability of the molding laminated sheet was good. The same mold as that used in Example 2 was used as the mold. Next, under conditions of a molding temperature of 200 to 240 ° C. and a mold temperature of 30 to 60 ° C., a polypropylene resin (containing 20% by mass of talc and 10% by mass of ethylene-propylene rubber) is used as a molding resin. Molding was performed. As a result, a molded product having the molded laminated sheet adhered to the surface of the molded product was obtained. The mold releasability of the molding laminated sheet was good. The molded article had no printing omission and good appearance. Next, the resin composition (A) was cured by irradiating the molded product with ultraviolet rays of about 600 mJ / cm ² using an ultraviolet irradiation device. As a result, a laminated molded article having high surface hardness and abrasion resistance, excellent gloss, a printed pattern, and excellent design properties was obtained.

Claims (11)

Applying a mixed solution containing the resin composition (A) and the solvent (S) on the acrylic resin base sheet (B);
A step of volatilizing the solvent (S) by heating and drying the acrylic resin base sheet (B), and forming a resin composition (A) layer on the acrylic resin base sheet (B);
A step of winding a laminated sheet comprising the resin composition (A) layer and the acrylic resin base sheet (B), and a method for producing a laminated sheet roll comprising:
The elongation percentage (L) of the acrylic resin base sheet (B) at the time of heating and drying calculated from the following formula (1) is 0.001% or more and 0.5% or less, and winding of the laminated sheet The tension (F2) per unit width of the laminated sheet at the time is 60 N / m or more and 170 N / m or less.
L = [F1 / (E * t * W)] * 100 (1)
(In Formula (1), F1: tension (N) applied to the acrylic resin base sheet (B) during heat drying, E: tensile elastic modulus in the flow direction of the acrylic resin base sheet (B) during heat drying ( MPa), t: thickness (mm) of the acrylic resin base sheet (B), W: width (mm) of the acrylic resin base sheet (B).   The method of Claim 1 which performs the process of laminating | stacking a protective film (C) on a resin composition (A) layer before the process of winding up a lamination sheet.   The method according to claim 2, wherein in the step of laminating the protective film (C), the temperature of the laminated sheet is 10 ° C or higher and 33 ° C or lower.   The resin composition (A) contains either an acrylic resin (a-1) having a radically polymerizable unsaturated group in the side chain and a photopolymerization initiator (a-2). The method according to one item.   The method according to claim 4, wherein the resin composition (A) further contains inorganic fine particles (a-3).   The method according to claim 5, wherein the inorganic fine particles (a-3) are colloidal silica.   The method according to any one of claims 4 to 6, wherein the resin composition (A) further contains a light stabilizer (a-4).   A laminated sheet roll produced by the method according to any one of claims 1 to 7.   The shaping | molding by which the at least 1 decoration layer chosen from a printing layer and a vapor deposition layer was laminated | stacked on the acrylic resin base-material sheet | seat (B) side surface of the lamination sheet unwound from the lamination sheet roll of Claim 8. Laminated sheet.   The laminated sheet for molding according to claim 9, wherein an adhesive layer is further laminated on the decorative layer.   The laminated sheet unwound from the laminated sheet roll according to claim 8 or the molded laminated sheet according to claim 9 or 10 is laminated so that the resin composition (A) layer becomes the outermost surface layer. Laminated molded product.