Laminate for thermoforming
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- MITSUBISHI GAS CHEM CO INC
- Filing Date
- 2025-11-14
- Publication Date
- 2026-06-19
Smart Images
Figure 2026100799000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a laminate for thermoforming, and particularly to a pre-cure type laminate for thermoforming.
Background Art
[0002] Plastic household appliances, in-vehicle products, etc. have generally been manufactured by coating plastic molded products as needed. However, since such methods have a large environmental impact, various methods have been studied, including the method of insert molding a thermoformable decorative film. In recent years, due to the increasing requirements for chemical resistance and scratch resistance of molded products, the demand for thermoforming laminates (e.g., films) with a hard coat has particularly increased. A thermoforming laminate with a hard coat is generally manufactured by applying a hard coat liquid onto a substrate and then curing it (Patent Document 1).
Prior Art Documents
Patent Documents
[0003]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0004] A hard coat layer that protects the surface of a laminate of resin films requires a certain degree of high scratch resistance and antifouling properties. On the other hand, in order to manufacture a resin film laminate having a desired shape, excellent formability is required for the resin films constituting each layer. And in the resin composition used particularly for the production of the hard coat layer of the laminate, it has been difficult to satisfy all of these different performances. An object of the present invention is to provide a pre-cure type laminate for thermoforming that is excellent in antifouling properties, cloth scratch resistance, etc. without deteriorating adhesion, chemical resistance, and coating film smoothness.
Means for Solving the Problems
[0005] As a result of diligent research to solve the above problems, the present inventors have found that by using a hard coat layer containing a urethane (meth)acrylate resin, a specific silicone-based leveling agent (B), and a photopolymerization initiator, a particularly pre-cure type thermoforming laminate with excellent stain resistance and fabric scratch resistance can be obtained, and have completed the present invention. That is, the present invention is as follows. <1> A thermoforming laminate comprising a base layer and a hard coat layer, The aforementioned base layer is formed by laminating a layer containing polycarbonate resin and a layer containing high-hardness resin. The thermoforming laminate is formed in which the hard coat layer is laminated on a layer containing a high-hardness resin in the base layer, the hard coat layer comprises a urethane (meth)acrylate resin (A), a silicone-based leveling agent (B) having a photocurable polymerization group, and a photopolymerization initiator (C), the weight-average molecular weight of the silicone-based leveling agent (B) is 2,000 or more and 15,000 or less, and the hard coat layer has a thickness of 1 to 10 μm. <2> The hard coat layer is pre-cured, <1> This is a thermoforming laminate as described above. <3> The above-mentioned base layer is obtained by melt-extruding polycarbonate resin and acrylic resin. <1> or <2> This is a thermoforming laminate as described above. <4> The content of the silicone-based leveling agent (B) is 0.1 to 5.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A), <1> from <3> It is a thermoforming laminate as described in any of the above. <5> The urethane (meth)acrylate resin (A) is a urethane (meth)acrylate resin having 6 to 10 functional groups, and its weight-average molecular weight is 2,000 to 12,000. <1> from <4> It is a thermoforming laminate as described in any of the above. <6> The urethane (meth)acrylate resin (A) has a structure obtained by reacting ethylene glycol with isophorone diisocyanate to produce a diisocyanate, and then further reacting this diisocyanate with pentaerythritol triacrylate. <1> from <5> It is a thermoforming laminate as described in any of the above. <7> The content of the photopolymerization initiator (C) is 2.0 to 7.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A), <1> from <6> It is a thermoforming laminate as described in any of the above. <8> The above high-hardness resin is a polymethyl methacrylate resin. <1> from <7> It is a thermoforming laminate as described in any of the above. <9> The hard coat layer further contains nanoparticles, the amount of which is 0.1 to 6.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A), <1> from <8> It is a thermoforming laminate as described in any of the above. <10> The hard coat layer further contains a light stabilizer, the amount of which is 0.1 to 4.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A), <1> from <9> It is a thermoforming laminate as described in any of the above. <11> The hard coat layer has a protective film on the surface opposite to the laminated surface with the base layer, and the base layer has a protective film on the surface opposite to the laminated surface with the hard coat layer, <1> from <10> It is a thermoforming laminate as described in any of the above. <12> The water contact angle of the surface of the hard coat layer is 100° or more. <1> from <11> It is a thermoforming laminate as described in any of the above. <13> On the surface of the aforementioned hard coat layer, Medigauze is applied at a rate of 500 gf / cm². 2 If abrasion occurs when reciprocating under pressure, and the object remains undamaged after 100 reciprocations, then the above <1> from <12> It is a thermoforming laminate as described in any of the above. [Effects of the Invention]
[0006] According to the present invention, it is possible to provide a pre-cure type thermoforming laminate with excellent stain resistance and fabric scratch resistance. Molded articles obtained from the thermoforming laminate of the present invention can be used, for example, as resin film laminates used in mobile devices, automotive interior components, home appliances, and the like. [Brief explanation of the drawing]
[0007] [Figure 1] This is a schematic cross-sectional view showing an example of a thermoforming laminate according to the embodiment. [Modes for carrying out the invention]
[0008] The components and manufacturing methods of the pre-cured thermoforming laminate according to the embodiment will be described in detail below. [1] Laminate for thermoforming The thermoforming laminate according to the embodiment includes a base layer and a hard coat layer. The base layer is formed by laminating a layer containing polycarbonate resin (hereinafter sometimes referred to as the "polycarbonate resin layer") and a layer containing high-hardness resin (hereinafter sometimes referred to as the "high-hardness resin layer"), and the hard coat layer is laminated on the high-hardness resin layer. In one preferred embodiment of the present invention, a protective film is provided on the surface of the hard coat layer opposite to the surface laminated with the substrate layer. In a further preferred embodiment, a protective film is provided on the surface of the hard coat layer opposite to the surface laminated with the substrate layer, and a protective film is provided on the surface of the substrate layer opposite to the surface laminated with the hard coat layer.
[0009] Figure 1 is a schematic cross-sectional view showing an example of a thermoforming laminate according to an embodiment. In Figure 1, the thermoforming laminate 10 has a structure in which a hard coat layer 16 is laminated on a base layer (a base layer consisting of a high-hardness resin layer 20 and a polycarbonate resin layer 22), and a protective film 12 is further laminated on top of that. That is, the surface of the hard coat layer 16 is protected by the protective film 12. An embodiment in which the protective film is laminated on the outer surface of the polycarbonate resin layer 22 is also preferred.
[0010] A thermoformable laminate according to a preferred embodiment of the present invention is of the pre-cured type. Therefore, the thermoformable laminate according to a preferred embodiment of the present invention comprises a cured hard coat layer. The means for curing the hard coat layer depends on the material of the hard coat layer, but examples include curing by active energy rays or heat. The thermoformable laminate according to the embodiment can be successfully molded with a protective film attached. Therefore, it is possible to prevent damage to the hard coat layer and the inclusion of foreign matter during molding. The following describes each layer of the thermoforming laminate according to the embodiment.
[0011] [2] Base material layer Preferably, the base layer is laminated so as to be in contact with the surface of the hard coat layer opposite to the protective film. However, it is not limited to this, and other layers may be placed between the base layer and the hard coat layer.
[0012] The base layer consists of a polycarbonate resin layer and a high-hardness resin layer laminated together. <Polycarbonate resin layer> The polycarbonate resin layer is a layer mainly containing a polycarbonate resin. The polycarbonate resin contained in the polycarbonate resin layer may be one type or two or more types. In the polycarbonate resin layer mainly composed of a polycarbonate resin, the proportion of the polycarbonate resin in the polycarbonate resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. By increasing the content of the polycarbonate resin, the impact resistance is improved.
[0013] The type of the polycarbonate resin is not particularly limited as long as it contains a carbonate ester bond -[O-R-OCO]-(R is an aliphatic group, an aromatic group, or a group containing both an aliphatic group and an aromatic group, and may have a linear structure or a branched structure) in the main chain of the molecule. Among them, a polycarbonate resin having a bisphenol skeleton is preferable, and a bisphenol A type polycarbonate resin having a bisphenol A skeleton or a bisphenol C type polycarbonate resin having a bisphenol C skeleton is particularly preferable. As the polycarbonate resin, a mixture of a bisphenol A type polycarbonate resin and a bisphenol C type polycarbonate resin, or a copolymer of bisphenol A and bisphenol C may be used. In order to improve the hardness of the polycarbonate resin layer, it is preferable to use a bisphenol C type polycarbonate resin (for example, a polycarbonate resin composed of bisphenol C, a mixture of a bisphenol A type polycarbonate resin and a bisphenol C type polycarbonate resin, or a copolymer of bisphenol A and bisphenol C).
[0014] <High-hardness resin layer> The high-hardness resin layer is a layer mainly containing a high-hardness resin. In this specification, the high-hardness resin is a resin having a higher hardness than the polycarbonate resin contained in the polycarbonate resin layer, and means a resin having a pencil hardness of HB or higher. The pencil hardness of the high-hardness resin is preferably HB to 3H, more preferably H to 3H, and particularly preferably 2H to 3H. The high-hardness resin contained in the high-hardness resin layer may be one type or two or more types. In the high-hardness resin layer mainly composed of a high-hardness resin, the proportion of the high-hardness resin to the high-hardness resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Specific examples of the high-hardness resin are not particularly limited, but for example, polymethyl methacrylate (PMMA), homopolymers of various (meth)acrylic acid esters represented by methyl methacrylate (MMA), or copolymers of PMMA, MMA, or monomers constituting them with one or more other monomers are preferably mentioned. Also, a mixture of a plurality of resins can be used. Among these, polymethyl methacrylate (PMMA) having a high surface hardness is particularly preferably mentioned. The weight average molecular weight of the acrylic resin is, for example, 40,000 to 200,000. The thickness of the high-hardness resin layer is preferably 10 to 100 μm, more preferably 12 to 80 μm, and even more preferably 15 to 70 μm. In the present invention, it is particularly preferable that the base material layer is obtained by melt co-extrusion of a polycarbonate resin and an acrylic resin.
[0015] The polycarbonate resin layer and the high-hardness resin layer may contain various thermoplastic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide as other resins.
[0016] The base layer used in the present invention is a laminate of a polycarbonate resin layer and a high-hardness resin layer, but is not limited to a two-layer structure and may have three or more layers. In the present invention, a hard coat layer is laminated on the high-hardness resin layer. By laminating a high-hardness resin layer and a hard coat layer, which have excellent weather resistance, on a polycarbonate resin layer, which has poor weather resistance, a film with excellent weather resistance can be obtained. Furthermore, by using a multilayer base layer containing a polycarbonate resin layer and a high-hardness resin layer, it is possible to improve the surface hardness of the base layer while maintaining the thermoformability of the base layer.
[0017] The viscosity-average molecular weight of the resin contained in the base layer is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and even more preferably 22,500 to 25,000.
[0018] The base layer may contain additives other than the resin mentioned above. Examples of additives include heat stabilizers, antioxidants, flame retardants, flame retardant enhancers, ultraviolet absorbers, mold release agents, and colorants, and the base layer may contain one or more of these. Furthermore, antistatic agents, fluorescent whitening agents, anti-fogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc., may be added to the base layer.
[0019] The thickness of the base layer, i.e., the total thickness of the polycarbonate resin layer and the high-hardness resin layer, is not particularly limited, but is preferably 0.10 mm to 1.0 mm. The thickness of the base layer is, for example, 0.15 mm to 0.80 mm, 0.18 mm to 0.60 mm, or 0.25 mm to 0.40 mm. By using a base layer of such thickness, a film with excellent moldability and hardness can be realized.
[0020] [3] Hard coat layer The hard coat layer comprises a urethane (meth)acrylate resin (A), a silicone-based leveling agent (B) having a photocurable polymerization group, and a photopolymerization initiator (C), wherein the weight-average molecular weight of the silicone-based leveling agent (B) is 2,000 to 15,000, and the hard coat layer has a thickness of 1 to 10 μm. By using such a hard coat layer, it is possible to form a pre-cure type thermoforming laminate with excellent stain resistance and fabric scratch resistance. The hard coat layer may further contain various additives to improve its properties, such as hindered amine light stabilizers, nanoparticles, other leveling agents, and ultraviolet absorbers.
[0021] (1) Urethane (meth)acrylate resin The hard coat layer contains a urethane (meth)acrylate resin. Preferably, the hard coat layer contains a urethane (meth)acrylate resin having 6 to 10 functional groups, and more preferably, a urethane (meth)acrylate resin having 6 to 8 functional groups. Specifically, examples include urethane (meth)acrylate resins that are copolymers of isocyanate compounds and acrylate compounds as described below. In this specification, (meth)acrylate means methacrylate and / or acrylate, and (meth)acryloyl group means methacryloyl group and / or acryloyl group. Other similar descriptions shall be interpreted as described above.
[0022] • Isocyanate compounds Examples of isocyanate compounds include aromatic isocyanates which may have alkyl substituents (such as methyl groups), preferably aromatic isocyanates having 6 to 16 carbon atoms, more preferably aromatic isocyanates having 7 to 14 carbon atoms, and particularly preferably aromatic isocyanates having 8 to 12 carbon atoms. While aromatic isocyanates are preferred as isocyanate compounds, aliphatic and alicyclic isocyanates are also preferably used.
[0023] Specific examples of isocyanate compounds include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1,3-bis(isocyanate). Examples include polyisocyanates such as cyclohexane, phenylenediisocyanate, lysine diisocyanate, lysine triisocyanate, and naphthalene diisocyanate; trimer or tetramer compounds of these polyisocyanates; biuret-type polyisocyanates; water-dispersible polyisocyanates (for example, "Aquanate 100," "Aquanate 110," "Aquanate 200," and "Aquanate 210" manufactured by Nippon Polyurethane Industries Co., Ltd.); and reaction products of these polyisocyanates with polyols.
[0024] Among these isocyanate compounds, particularly preferred are diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, trimethylolpropane (TMP) adduct of toluene diisocyanate, isocyanate of toluene diisocyanate, TMP adduct of xylene diisocyanate, and dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), etc., represented by the following formula. [ka]
[0025] • Acrylates Examples of acrylate compounds for forming urethane (meth)acrylate resins containing a cyclic molecular structure include pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), and hydroxypropyl acrylate (HPA). Furthermore, as the acrylate compound, a compound having both a (meth)acryloyloxy group and a hydroxyl group, such as a monofunctional (meth)acrylic compound having a hydroxyl group, can also be used.
[0026] Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include hydroxyl group-containing mono(meth)acrylates {e.g., hydroxyalkyl (meth)acrylates [e.g., hydroxyC2-20 alkyl-(meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, preferably hydroxyC2-12 alkyl-(meth)acrylate, more preferably hydroxyC2-6 alkyl-(meth)acrylate], polyalkylene glycol mono(meth)acrylates [e.g., polyC2-4 alkylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate], and three or more hydroxyl groups. Examples include mono(meth)acrylates of polyols having a syl group [e.g., mono(meth)acrylates of alkane polyols such as glycerin mono(meth)acrylate and trimethylolpropane mono(meth)acrylate, and mono(meth)acrylates of polymers of alkane polyols such as diglycerin mono(meth)acrylate], N-hydroxyalkyl(meth)acrylamides (e.g., N-hydroxyC1-C4 alkyl(meth)acrylamides such as N-methylol(meth)acrylamide and N-(2-hydroxyethyl)(meth)acrylamide), and adducts obtained by adding a lactone (e.g., a C4-C10 lactone such as ε-caprolactone) to the hydroxyl group of these compounds (e.g., hydroxyalkyl(meth)acrylates) (e.g., adducts with approximately 1-5 moles of lactone added). These acrylate compounds may be used individually or in combination of two or more.
[0027] A preferred specific example of a compound for forming a (meth)acryloyloxy group is 2-hydroxy-3-phenoxypropyl acrylate. Among those mentioned above, pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), and hydroxypropyl acrylate (HPA) are particularly preferred.
[0028] • Copolymer of isocyanate compounds and acrylate compounds Preferred specific examples of copolymers of isocyanate compounds and acrylate compounds, i.e., urethane (meth)acrylate resins, include copolymers of xylylene diisocyanate (XDI) and pentaerythritol triacrylate (PETA), copolymers of XDI and dipentaerythritol pentaacrylate (DPPA), copolymers of dicyclohexylmethane diisocyanate (H12MDI) and PETA, copolymers of isophorone diisocyanate (IPDI) and PETA, and copolymers of XDI and hydroxypropyl (meth)acrylate (HPA).
[0029] Furthermore, as urethane (meth)acrylate resins containing a cyclic molecular structure, copolymers using polyol compounds, in addition to the isocyanate compounds and acrylate compounds mentioned above, can also be cited. Polyol compounds (polyhydric alcohols) are compounds having two or more hydroxyl groups in one molecule, and examples include the following:In other words, examples of polyol compounds include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, and 2,3-dimethyl Dihydric alcohols such as limethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, and neopentyl glycol hydroxypivalate; polylactones obtained by adding lactones such as ε-caprolactone to these dihydric alcohols. Examples include diols; ester diols such as bis(hydroxyethyl) terephthalate; polyether diols such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol; α-olefin epoxides such as propylene oxide and butylene oxide; monoepoxy compounds such as Cardura E10 [manufactured by Shell Chemical, a synthetic highly branched saturated fatty acid glycidyl ester]; trihydric or higher alcohols such as glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, and mannitol; polylactone polyols obtained by adding lactones such as ε-caprolactone to these trihydric or higher alcohols; and alicyclic polyhydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F.
[0030] A urethane (meth)acrylate resin containing a constituent unit derived from tricyclodidecanedimethanol (TCDDM), represented by the following formula, is preferably used as the polyol constituent unit. [ka]
[0031] Preferred specific examples of urethane (meth)acrylate resins containing polyol constituent units include copolymers of tricyclodidecanedimethanol (TCDDM), IPDI, and PETA; copolymers of TCDDM, H12MDI, and PETA; copolymers of these copolymers in which DPPA is used instead of PETA, or in combination with PETA; and copolymers of TCDDM, xylylene diisocyanate (XDI), and hydroxypropyl (meth)acrylate (HPA).
[0032] A urethane (meth)acrylate resin containing isocyanate compounds, compounds having (meth)acryloyloxy and hydroxyl groups, and structural units derived from polyol compounds preferably contains at least one component represented by the following formula (i). (A3)-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3) ···(i) (In equation (i), A1 is an alkylene group derived from the polyol compound mentioned above, A2 is an alkylene group derived from the above-mentioned isocyanate compound, A3 is an alkyl group derived independently from the compound having the (meth)acryloyloxy group and the hydroxyl group described above. Examples of compounds used to form A3 include 2-hydroxy-3-phenoxypropyl acrylate.
[0033] In urethane (meth)acrylate resins, the ratio of constituent units derived from compounds having (meth)acryloyloxy groups and hydroxyl groups to constituent units derived from isocyanate compounds is preferably 99:1 to 30:70 (by weight), more preferably 97:3 to 60:40, and even more preferably 95:5 to 80:20.
[0034] (Urethane (meth)acrylate resin containing acrylate) A preferred example of a urethane (meth)acrylate resin is one that includes structural units derived from urethane (meth)acrylate and structural units derived from (meth)acrylate. A more preferred example of such a urethane (meth)acrylate resin is one that includes structural units derived from hexafunctional urethane (meth)acrylate and structural units derived from difunctional (meth)acrylate.
[0035] • (6-functional) urethane acrylate As described above, the urethane (meth)acrylate resin preferably contains constituent units derived from urethane (meth)acrylate, particularly hexafunctional urethane (meth)acrylate. Preferred examples of hexafunctional urethane acrylates include those represented by the following formulas, namely, reaction products of dicyclohexylmethane diisocyanate (H12MDI) and pentaerythritol triacrylate (PETA), and reaction products of isophorone diisocyanate (IPDI) and PETA. Specific examples of preferred products of these hexafunctional urethane acrylates include CN-968 (reaction product of IPDI and PETA: manufactured by Sartomer Japan Co., Ltd.) and CN-975 (manufactured by Sartomer Japan Co., Ltd.). [ka] [ka]
[0036] • (Meth)acrylate (bifunctional (meth)acrylate, etc.) The (meth)acrylate constituent units that can constitute the urethane (meth)acrylate resin are preferably constituent units derived from a compound having 4 to 20 carbon atoms, which may have substituents, and which contain at least one (meth)acryloyloxy group and at least one vinyl ether group. The number of carbon atoms in the (meth)acrylate is preferably 6 to 18, more preferably 8 to 16. Examples of substituents in the (meth)acrylate include alkyl groups. Furthermore, the (meth)acrylate is preferably difunctional. As the (meth)acrylate, for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate:VEEA] of the following formula is preferably used. [ka] (In the above formula, R is either a hydrogen atom or a methyl group.)
[0037] In urethane (meth)acrylate resin, the ratio of constituent units derived from urethane acrylate to constituent units derived from (meth)acrylate is preferably 99:1 to 30:70 (by weight), more preferably 97:3 to 60:40, and even more preferably 95:5 to 80:20.
[0038] (Fluorine-containing urethane (meth)acrylate resin) A fluorine-containing urethane acrylate resin may be used as the urethane (meth)acrylate resin. The fluorine-containing urethane acrylate resin preferably contains at least the component represented by the following formula (ii). (A3)-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3)...(ii) In the above formula (ii), A1 is preferably an alkylene group derived from a fluorine-containing diol having 8 or fewer carbon atoms, which may have substituents, and the number of carbon atoms is preferably 6 or less, for example, 1 to 4. Examples of substituents included in the alkylene group of A1 include alkyl groups.
[0039] In formula (ii) above, A2 is independently an alkylene group derived from an aliphatic or alicyclic isocyanate having 4 to 20 carbon atoms, which may have substituents. The number of carbon atoms in A2 is preferably 6 to 16, and more preferably 8 to 12. Examples of substituents on the alkylene group of A2 include alkyl groups. Furthermore, an example of an alicyclic isocyanate that forms A2 is isophorone diisocyanate, as shown in the formula below. [ka]
[0040] In formula (ii) above, A3 is an alkyl group having 4 to 30 carbon atoms, each independently containing at least one (meth)acryloyloxy group and possibly having substituents. The number of carbon atoms in A3 is preferably 6 to 20, and more preferably 8 to 16. Examples of substituents on the alkyl group of A3 include branched alkyl groups. A3 preferably contains at least two (meth)acryloyloxy groups, and may contain, for example, three (meth)acryloyloxy groups. Furthermore, A3 is derived, for example, from pentaerythritol triacrylate, as shown in the following formula. [ka]
[0041] The fluorine-containing urethane acrylate resin is preferably formed from the compounds described above, and the fluorine-containing urethane acrylate includes, for example, the compound represented by the following formula (IV). [ka]
[0042] In a preferred embodiment of the present invention, a urethane (meth)acrylate resin is used that has a structure obtained by reacting ethylene glycol with isophorone diisocyanate to produce a diisocyanate, and then further reacting that with pentaerythritol triacrylate.
[0043] Other active energy ray curing resins The hard coat layer may contain active energy ray curable resins or thermosetting resins other than urethane (meth)acrylate resins, to the extent that the effects of the present invention are not impaired. Any resin that is curable by active energy rays can be used as the active energy ray curable resin. Examples of active energy ray curable resins include epoxy (meth)acrylate polymers and polyester (meth)acrylate polymers. In particular, polymers having (meth)acryloyl groups, such as epoxy (meth)acrylate polymers having (meth)acryloyl groups and polyester (meth)acrylate polymers having (meth)acryloyl groups, can be used. Active energy ray curable resins are readily available from various manufacturers. Furthermore, as active energy ray curable resins, for example, (meth)acrylate polymers that do not contain (meth)acryloyl groups, or (meth)acrylate polymers that do not contain a (meth)acrylate skeleton, can also be used. In addition, as active energy ray curable resins, substances other than (meth)acrylate compounds, such as epoxy compounds and oxetane compounds, can also be used.
[0044] The hard coat layer may contain one type of resin or two or more types. The resin content in the hard coat layer is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 90% by mass, when the total amount of components contained in the hard coat layer is taken as 100% by mass.
[0045] The urethane (meth)acrylate resin used in the present invention preferably has a weight-average molecular weight of 2,000 to 12,000, more preferably 4,000 to 10,000, even more preferably 5,000 to 9,000, and particularly preferably 6,000 to 8,000. By using a urethane (meth)acrylate resin with such a weight-average molecular weight, a thermoforming laminate with excellent moldability and scratch resistance can be obtained. The weight-average molecular weight can be measured based on the description in paragraphs
[0061] to
[0064] of Japanese Patent Publication No. 2007-179018. Details of the measurement method are shown below. [Table 1]
[0046] Specifically, first, a calibration curve showing the relationship between elution time and the molecular weight of the polymer is created using a universal calibration method with polystyrene as the standard polymer. Then, the elution curve (chromatogram) of the urethane (meth)acrylate resin is measured under the same conditions as the calibration curve described above. Furthermore, the weight-average molecular weight (Mw) is calculated from the elution time (molecular weight) and the peak area (number of molecules) of the urethane (meth)acrylate resin. The weight-average molecular weight is expressed by the following formula (A), where Ni represents the number of molecules with molecular weight Mi. Mw = Σ(NiMi) 2 ) / Σ(NiMi)····(A)
[0047] (2) Silicone-based leveling agent having a photocurable polymer group The hard coat layer contains a silicone-based leveling agent having a photocurable polymerization group. This improves the leveling, stain resistance, and abrasion resistance of the hard coat layer. The weight-average molecular weight of the silicone-based leveling agent used in the present invention is 2,000 to 15,000, preferably 4,000 to 14,000, more preferably 6,000 to 13,000, and particularly preferably 8,000 to 12,000. If the weight-average molecular weight of the silicone-based leveling agent is less than 2,000, water repellency and slipperiness may not be achieved, and if it exceeds 15,000, compatibility with the resin may deteriorate, resulting in an uneven coating film. The weight-average molecular weight of silicone-based leveling agents can be determined by the GPC method under the following conditions. Analytical instrument: LC-20AD System (manufactured by Shimadzu Corporation) Columns: LF-G (Shodex), LF-804L (Shodex) Detector: Suggestive refractometer Column temperature: 40℃ Developing solvent: Toluene Reference material: Polystyrene Flow rate: 1.0mL / min Injection volume: 100μL
[0048] Silicone-based compounds included in silicone-based leveling agents include compounds having polyalkylsiloxane bonds. While silicone-based leveling agents can be synthesized by oneself, commercially available products are readily available. For example, the KP series from Shin-Etsu Chemical Co., Ltd., the BYK series from BIC Chemie Japan, and the TEGO Glide series from EVONIK are available. More specifically, the silicone-based leveling agents described in the examples below are examples, such as polyether-modified polydimethylsiloxane BYK-UV3500 from BIC Chemie Japan and RS-57 from DIC.
[0049] The content of the silicone-based leveling agent is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 4.0 parts by mass, and particularly preferably 1.0 to 2.0 parts by mass, per 100 parts by mass of urethane (meth)acrylate resin. If the content of silicone-based leveling agent is less than 0.1 parts by mass, water repellency and slipperiness may not be achieved, and if it exceeds 5.0 parts by mass, compatibility with the resin may deteriorate, resulting in an uneven coating film.
[0050] In this invention, a silicone-based leveling agent is used, but a fluorine-based leveling agent may also be included, as long as it does not impair the effects of the present invention. Examples of fluorine-based compounds included in the fluorine-based leveling agent include compounds having a perfluoropolyether bond. Fluorine-based leveling agents can be synthesized by oneself, but commercially available products are readily available. For example, DIC's Megafac RS series, Shin-Etsu Chemical's KY series (which is also a silicone-based leveling agent), and Daikin's Optool series can be used. In one embodiment of the present invention, from the viewpoint of fabric scratch resistance, the hard coat layer contains a photopolymerization initiator and a silicone-based leveling agent having a photocurable polymerization group, but it is preferable that it does not contain a fluorine-based leveling agent having a photocurable polymerization group. In particular, from the viewpoint of PFAS regulations, it is preferable that it does not contain fluorine compounds.
[0051] (3) Photopolymerization initiator The urethane (meth)acrylate resin contained in the hard coat layer is either active energy ray curable or thermosetting. Therefore, the hard coat layer contains a photopolymerization initiator. Examples of photopolymerization initiators include IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone), IRGACURE 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one), IRGACURE TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), and EsacureONE (oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone)). Among these, Esacure One is preferred as a photopolymerization initiator from the viewpoint of heat resistance.
[0052] The content of the photopolymerization initiator in the hard coat layer is preferably 2.0 to 7.0 parts by mass, more preferably 2.5 to 6.5 parts by mass, and particularly preferably 3.0 to 6.0 parts by mass, per 100 parts by mass of urethane (meth)acrylate resin.
[0053] (4) Hindered amine light stabilizers The hard coat layer may contain a hindered amine-based light stabilizer. The content of the hindered amine-based light stabilizer in the hard coat layer is preferably 0.1 to 4.0 parts by mass, more preferably 0.3 to 3.5 parts by mass, and even more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of urethane (meth)acrylate resin.
[0054] In one preferred embodiment of the present invention, the hindered amine-based light stabilizer includes a compound represented by the following general formula (1). [ka] In general formula (1), R1 represents a hydrogen atom, an alkyl group, or an alkoxy group, preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 6 to 13 carbon atoms. In general formula (1), R2 represents a hydrocarbon-containing group or an ether group, and the hydrocarbon-containing group may have substituents such as a phenyl group. Preferably, R2 represents an alkylene group or an ether group having -OC(=O)-.
[0055] In a preferred embodiment of the present invention, the hindered amine-based light stabilizer comprises at least one compound selected from the group of compounds represented by the following structural formula. [ka]
[0056] In the present invention, Tinuvin 123 (manufactured by BASF), Tinuvin 770DF (manufactured by BASF), Tinuvin 144 (manufactured by BASF), LA-81 (manufactured by ADEKA), Tinuvin 152 (manufactured by BASF), Tinuvin 292 (manufactured by BASF), etc., can be preferably used as hindered amine light stabilizers. These may be used individually or in combination of two or more.
[0057] (5) Nanoparticles The hard coat layer may contain nanoparticles. This can improve the scratch resistance and hardness of the hard coat layer. The nanoparticles may be inorganic or organic, but inorganic nanoparticles are preferred, and inorganic oxide nanoparticles are more preferred. For example, metal oxide nanoparticles such as nanosilica, nanoalumina, nanotitania, and nanozirconia can be used. Nanodiamonds may also be used.
[0058] The hard coat layer preferably contains alumina particles or silica particles as nanoparticles. The nanoparticles contained in the hard coat layer are preferably treated with a surface treatment agent. Surface treatment allows the inorganic nanoparticles to be stably dispersed in the hard coat composition, particularly in the urethane (meth)acrylate resin.
[0059] As a surface treatment agent for nanoparticles, compounds having substituents that can bond to the surface of nanoparticles and substituents that have high compatibility with the components of the hard coat layer that disperses the nanoparticles (e.g., urethane (meth)acrylate resin, etc.) are preferably used. For example, silane compounds, alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, etc. can be used as surface treatment agents.
[0060] Inorganic nanoparticles preferably have polymerizable groups on their surface. Polymerizable groups can be introduced by surface treatment of inorganic nanoparticles, and specific examples of polymerizable groups include vinyl groups, meth(acrylic) groups, and free radical polymerizable groups. The average particle diameter of the nanoparticles is preferably 1 to 150 nm, more preferably 10 to 100 nm, and particularly preferably 15 to 50 nm. The average particle diameter of the nanoparticles can be measured by observing a cross-section of the hard coat layer with an electron microscope. For example, the average particle diameter can be obtained by taking a TEM image of a particle cross-section prepared by FIB processing, measuring the diameter of 50 observed particles, and calculating the average value. If the particles are not spherical, the average of the major and minor axes is considered to be the diameter of that particle.
[0061] The hard coat layer preferably contains 0.1 to 6.0 parts by mass of nanoparticles, such as inorganic nanoparticles, per 100 parts by mass of urethane (meth)acrylate resin. More preferably, it contains 1.0 to 5.0 parts by mass of inorganic nanoparticles, and particularly preferably, 1.5 to 4.0 parts by mass of inorganic nanoparticles.
[0062] (6) UV absorbers The hard coat layer may contain an ultraviolet absorber. This can suppress the deterioration of the urethane (meth)acrylate resin due to ultraviolet irradiation during weathering tests. Suitable ultraviolet absorbers include DAINSORB-T0 (manufactured by Yamato Kasei Co., Ltd.), Tinuvin405 (manufactured by BASF), Tinuvin477 (manufactured by BASF), Tinuvin479 (manufactured by BASF), Tinuvin928 (manufactured by BASF), UVA-903KT (manufactured by BASF), etc. The amount of ultraviolet absorber in the hard coat layer is preferably 0.1 to 4.0 parts by mass, more preferably 0.3 to 3.5 parts by mass, and even more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of urethane (meth)acrylate resin.
[0063] (7) Other additives The hard coat layer may contain other additives, such as heat stabilizers, antioxidants, flame retardants, flame retardant enhancers, mold release agents, colorants, etc. Antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc., may be added to the hard coat layer as long as they do not significantly impair the desired physical properties.
[0064] The diluent used in preparing the hard coat composition is used to adjust the viscosity and can be used without particular limitations as long as it is nonpolymerizable. By using a diluent, the hard coat composition can be easily applied onto the substrate layer.
[0065] Examples of diluent solvents include toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellsolve, ethyl cellsolve, ethyl cellsolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.
[0066] <Manufacturing of the hard coat layer> The hard coat layer is manufactured by applying a hard coat composition containing the materials described above onto a high-hardness resin layer in a substrate layer. For example, the hard coat composition can be prepared by mixing each material and further stirring it with a disperser.
[0067] Examples of methods for applying the hard coat composition include using a bar coater, gravure coater, die coater, dip coat, and spray coat. After applying the hard coat composition, it is dried at a predetermined temperature. The drying temperature is preferably 30 to 150°C, and more preferably 60 to 130°C. By drying at a temperature within this range, organic solvents can be removed from the hard coat layer, and deformation of other layers due to heating can be prevented.
[0068] The thickness of the hard coat layer is 1 to 10 μm, preferably 2 to 7 μm. By setting the thickness within this range, the desired performance of the hard coat layer can be obtained, and problems with adhesion and moldability are less likely to occur.
[0069] In the present invention, the water contact angle of the hard coat layer surface is preferably 100° or more, more preferably 102° or more, and particularly preferably 104° or more. The water contact angle can be measured by the method described in the examples below.
[0070] In this invention, Medigauze is applied to the surface of the hard coat layer at a concentration of 500 gf / cm². 2 When subjected to abrasion by reciprocating under pressure, it is preferable that the object remains undamaged after 100 reciprocations, and more preferably that it remains undamaged after 1000 reciprocations.
[0071] [4] Protective film It is preferable to place a protective film on the surface of the hard coat layer to prevent damage to the hard coat layer surface during the molding process, etc. Furthermore, it is preferable to place a protective film on the outer surface of the base layer as well. The protective film is attached to the surface of the hard coat layer after, for example, the hard coat composition has been applied to the base layer and dried. It is preferable that the surface of the protective film that is in contact with the hard coat layer is an adhesive surface with appropriate adhesive strength so that it can be attached to the surface of the hard coat layer. The structure of the protective film is not particularly limited, but it is preferable to be a single-layer film consisting only of an adhesive layer, or a film having a two-layer structure of a base material and an adhesive layer. In the case of a two-layer protective film, the adhesive surface of the adhesive layer is laminated on the hard coat layer so that it is in contact with the hard coat layer. The protective film may also have a multilayer structure that includes layers other than the base material and adhesive layer described above. The protective film may also have a single-layer structure, and even in the case of a single-layer protective film, the adhesive surface, which is the surface facing the hard coat layer, has appropriate adhesive strength.
[0072] If the protective film has a substrate, the substrate preferably contains a thermoplastic resin, and more preferably a polyolefin resin. Examples of polyolefin resins included in the protective film are polyethylene, polypropylene, etc., and may be homopolymers or copolymers. Among polyolefin resins, polyethylene is preferred. As polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), etc. can be used, but low-density polyethylene is preferred.
[0073] Furthermore, as polyolefin copolymers, copolymers of ethylene or propylene and monomers copolymerizable with these can be used. Examples of monomers copolymerizable with ethylene or propylene include α-olefins, styrenes, dienes, cyclic compounds, and oxygen atom-containing compounds.
[0074] Examples of α-olefins include 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Examples of styrenes include styrene, 4-methylstyrene, and 4-dimethylaminostyrene. Examples of dienes include 1,3-butadiene, 1,5-hexadiene, 1,4-hexadiene, and 1,7-octadiene. Examples of cyclic compounds include norbornene and cyclopentene. Examples of oxygen atom-containing compounds include hexenol, hexenoic acid, and methyl octenoate. These copolymerizable monomers may be used individually or in combination of two or more types. They may also be copolymers of ethylene and propylene. Furthermore, the copolymer may be formed by alternating copolymerization, random copolymerization, or block copolymerization.
[0075] The polyolefin resin contained in the substrate of the protective film may also contain a modified polyolefin resin that has been modified with a small amount of carboxyl group-containing monomers such as acrylic acid, maleic acid, methacrylic acid, maleic anhydride, fumaric acid, and itaconic acid. Modification is usually possible by copolymerization or graft modification.
[0076] The content of thermoplastic resin (e.g., polyolefin resin) in the substrate of the protective film is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the substrate.
[0077] The adhesive layer of the protective film preferably contains an elastomer or a thermoplastic resin. Examples of thermoplastic resins included in the adhesive layer include polyolefin resins such as polyethylene and polypropylene, and may be either homopolymers or copolymers. Among polyolefin resins, polyethylene is preferred.
[0078] The elastomer or thermoplastic resin content in the adhesive layer of the protective film is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the adhesive layer.
[0079] The thickness of the protective film is preferably 10 to 100 μm, more preferably 20 to 80 μm. Even if the protective film consists of two or more layers, it is preferable that the sum of the thicknesses of each layer is within the above range.
[0080] In the case of protective films, it is preferable that the surface roughness Sa value (ISO 25178) of the adhesive surface that comes into contact with the hard coat layer before being attached to the hard coat layer (unattached) is 0.100 μm or less. More preferably, the surface roughness Sa value of the adhesive surface of the protective film in the unattached state is 0.090 μm or less, even more preferably 0.080 μm or less, and particularly preferably 0.070 μm or less.
[0081] The adhesive strength value on the adhesive surface of the protective film is preferably 5 (mN / 25mm) or more and 5000 (mN / 25mm) or less relative to the surface of the PMMA (high-hardness resin layer), and more preferably 9 (mN / 25mm) or more and 3000 (mN / 25mm) or less.
[0082] [5] Method for manufacturing a laminate for thermoforming The thermoforming laminate according to the embodiment is manufactured as follows. First, the base material is processed into a layered (sheet-like) form using conventional methods to produce the base layer. For example, extrusion molding, casting, etc., can be used. An example of extrusion molding is a method in which pellets, flakes, or powder of a resin composition are melted and kneaded in an extruder, then extruded from a T-die or the like, and the resulting semi-molten sheet is cooled and solidified while being pressed between rolls to form a sheet. Then, a hard coat composition obtained by mixing the above-mentioned materials is applied to the outer surface of the high-hardness resin layer of the substrate layer having multiple layers (polycarbonate resin layer and high-hardness resin layer) to form a hard coat layer. Furthermore, if necessary, the protective film described above is laminated onto the hard coat layer to manufacture a thermoforming laminate. It is also preferable to laminate the protective film described above onto the outer surface of the base layer. [Examples]
[0083] The present invention will be described in detail below with reference to examples, but the content of the present invention is not limited thereto.
[0084] <Appearance after coating (compatibility with resin)> The hard coat composition was evaluated by observing its appearance when applied to a high-hardness resin layer on a substrate layer. ○: No abnormalities in appearance. ×: External abnormalities such as streaks and imperfections present.
[0085] <Chemical Resistance Test> Neutrogena SPF100 (manufactured by Johnson & Johnson) was applied to the hard coat layer, and the appearance was visually observed after 1 hour at 80°C. ○: No change in appearance △: Swelling on the surface ×: Surface whitening present
[0086] <Adhesion Test> The adhesion of the hard coat layer to the substrate was evaluated according to the evaluation method of JIS K5600-5-6:1999. 〇:Classification 0 ×: Classification 1 or higher
[0087] <Moldability> The moldability was evaluated using a pressure molding machine. A test specimen was placed in a cube-shaped lower mold with a deep drawing height of 5-7 mm and dimensions of 30 mm in both length and width, so that the surface of the polycarbonate resin side of the base layer was in contact with it. The film temperature was heated to 180°C in the heating space, and compressed air at 2.5 MPa was applied to the test specimen in the molding space to form it into close contact with the convex part of the lower mold. ○: No cracks in the 5mm high cube mold. ×: Cracks present in the 5mm high cube mold.
[0088] <Fabric abrasion resistance test> The test specimen was treated with Medigauze (manufactured by Osaki Medical Co., Ltd.) at a concentration of 500 gf / cm³. 2 The hard coat layer was abraded by moving the tool back and forth under pressure. The presence or absence of scratches was visually determined, and the abrasion resistance was evaluated according to the evaluation criteria below. 〇: No damage after 1000 round trips. △: No damage after 100 round trips. ×: One or more scratches in 100 round trips
[0089] <Water contact angle> A contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement. A 2 μL droplet of water was dropped onto the hard coat layer, and the contact angle after 1 second was measured using the fitting method (Height Width Automatic method (θ / 2 method)). The average value of N=5 was taken as the average contact angle of water. ○: Water contact angle is 104° or higher △: Water contact angle is between 100° and 104° ×: Water contact angle is less than 100°
[0090] <Stain-resistant performance test> Two μl of oleic acid was dropped onto the hard coat layer as an artificial fingerprint solution, spread with a silicone pad, and then a cloth was attached and passed over the artificial fingerprint solution completely. This operation was repeated up to a maximum of 10 times until no fingerprints were visible to the naked eye, and the stain resistance was evaluated based on the number of repetitions according to the evaluation criteria below. ○: Fingerprint wiping count is less than 5 times △: Number of times fingerprints have been wiped off is between 5 and 10. ×: Fingerprints remain even after wiping them off 10 times.
[0091] <SW scratch resistance test> The test specimen was coated with #0000 steel wool at a density of 100 gf / cm². 2 The hard coat layer was abraded by 15 reciprocating motions under pressure. The haze change (ΔH) of the hard coat layer before and after abrasion was measured according to JIS K 7136:2000, and the abrasion resistance was evaluated according to the following evaluation criteria. ○: ΔH is less than 5% △: ΔH is between 5% and less than 10% ×: ΔH is 10% or more
[0092] <Weather resistance test> Using an ATLAS Ci4000 model, the test was conducted in accordance with the SAE J2412 standard for a total test duration of 504 hours (cumulative dose: 790 kJ / m²). 2 A test was conducted at a control wavelength of 340 nm. The test conditions are shown in the table below. After the test, the appearance was visually inspected. [Table 2] ○: No abnormalities in appearance. ×: Surface whitening present
[0093] (Example 1) To 100 parts by mass of urethane (meth)acrylate resin (manufactured by Negami Kogyo Co., Ltd., model number H-340, weight-average molecular weight 6,500, number of functional groups 6), 0.3 parts by mass of silicone-based leveling agent (manufactured by DIC, RS-57), 4 parts by mass of photopolymerization initiator ESACURE-ONE, and 1 part by mass of hindered amine-based light stabilizer (manufactured by BASF, Tinuvin 123) were added. Subsequently, propylene glycol monomethyl ether was added as a diluent to a solid content concentration of 13% by mass and stirred to obtain a hard coat composition. As the base layer, a two-layer product of bisphenol A type polycarbonate resin and PMMA, DF02U (manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 0.254 mm, PMMA thickness 0.055 mm), was prepared. Using a wire bar coater, the hard coat composition obtained above was applied to the PMMA side of the base layer to a film thickness of 3 μm after drying. After drying the hard coat composition at 80°C for 3 minutes, it was treated with an ultraviolet irradiation unit (manufactured by Heraeus) at 200 mJ / cm². 2 A laminate for thermoforming was fabricated by irradiating it with ultraviolet light. The table below shows the results of evaluating various physical properties of the obtained thermoforming laminate.
[0094] (Examples 2-19, Comparative Examples 1-8) A thermoformable laminate was prepared in the same manner as in Example 1, except that the components shown in the table below were used in the amounts shown in the table below. The results of evaluating various physical properties of the obtained thermoformable laminate are shown in the table below.
[0095] [Table 3] [Table 4]
[0096] <Explanation of ingredients in the table> Urethane (meth)acrylate resin (H-340): Manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight 6500, number of functional groups 6 Urethane (meth)acrylate resin (UN-952): Manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight 9500, number of functional groups 10 Urethane (meth)acrylate resin (UN-954): Manufactured by Negami Kogyo Co., Ltd., weight-average molecular weight 4200, number of functional groups 6 Urethane (meth)acrylate resin (EBECRYL8402): Manufactured by Daicel Ornex Corporation, weight-average molecular weight 1000, number of functional groups 2 Silicone-based leveling agent (RS-57): Manufactured by DIC Corporation Silicone-based leveling agent (KP-423): Manufactured by Shin-Etsu Chemical Co., Ltd., organically modified polydimethylsiloxane Silicone-based leveling agent (TEGO RAD2250): Manufactured by Evonik Industries, Ltd., organically modified silicone. Silicone-based leveling agent (BYK-333): Manufactured by BIC Chemie Japan Co., Ltd., polyether-modified polydimethylsiloxane Silicone-based leveling agent (BYK-UV3500): Manufactured by Bic Chemie Japan Co., Ltd., polyether-modified polydimethylsiloxane Silicone-based leveling agent (BYK-UV3575): Manufactured by Bic Chemie Japan Co., Ltd., polyether-modified polydimethylsiloxane Silicone-based leveling agent (BYK-UV3570): Manufactured by Bic Chemie Japan Co., Ltd., polyester-modified polydimethylsiloxane Silicone-based leveling agent (KP-410): Manufactured by Shin-Etsu Chemical Co., Ltd., containing polydimethylsiloxane. Silicone-based leveling agent (KP-411): Manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane Silicone-based leveling agent (KP-422): Manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane Silicone-based leveling agent (KP-415): Manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane Silicone-based leveling agent (KP-420): Manufactured by Shin-Etsu Chemical Co., Ltd., containing polydimethylsiloxane. Fluorine-based silicone leveling agent (KY-1203): Manufactured by Shin-Etsu Chemical Co., Ltd. Nanoparticles (NANOBYK-3605): Manufactured by BIC Chemie Japan Co., Ltd., nanosilica, average particle size 20-25 nm Nanoparticles (NANOBYK-3601): Manufactured by BIC Chemie Japan Co., Ltd., nanoalumina, average particle size 40 nm Nanoparticles (NANOBYK-3611): Manufactured by BIC Chemie Japan Co., Ltd., nanoalumina, average particle size 20-25 nm [ka] Hindered amine light stabilizer (Tinuvin 123): Manufactured by BASF.
[0097] While several embodiments of the present invention have been described, these embodiments are presented as examples only and are not intended to limit the scope of the invention. These novel embodiments can be carried out in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents. [Explanation of symbols]
[0098] 10: Laminate for thermoforming 12: Protective film 16: Hard court layer 20: High hardness resin layer (base material layer) 22: Polycarbonate resin layer (base layer)
Claims
1. A thermoforming laminate comprising a base layer and a hard coat layer, The aforementioned base layer is formed by laminating a layer containing polycarbonate resin and a layer containing high-hardness resin. The thermoforming laminate is characterized in that the hard coat layer is laminated on a layer containing a high-hardness resin in the base layer, the hard coat layer comprises a urethane (meth)acrylate resin (A), a silicone-based leveling agent (B) having a photocurable polymerization group, and a photopolymerization initiator (C), the weight-average molecular weight of the silicone-based leveling agent (B) is 2,000 or more and 15,000 or less, and the hard coat layer has a thickness of 1 to 10 μm.
2. The thermoforming laminate according to claim 1, wherein the hard coat layer is pre-cured.
3. The thermoforming laminate according to claim 1 or 2, wherein the base layer is obtained by melt-extruding a polycarbonate resin and an acrylic resin.
4. The thermoforming laminate according to any one of claims 1 to 3, wherein the content of the silicone-based leveling agent (B) is 0.1 to 5.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A).
5. The thermoforming laminate according to any one of claims 1 to 4, wherein the urethane (meth)acrylate resin (A) is a urethane (meth)acrylate resin having 6 to 10 functional groups and having a weight-average molecular weight of 2,000 to 12,000.
6. The thermoforming laminate according to any one of claims 1 to 5, wherein the urethane (meth)acrylate resin (A) has a structure obtained by reacting ethylene glycol with isophorone diisocyanate to produce a diisocyanate, and then further reacting pentaerythritol triacrylate with that diisocyanate.
7. The thermoforming laminate according to any one of claims 1 to 6, wherein the content of the photopolymerization initiator (C) is 2.0 to 7.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A).
8. The thermoforming laminate according to any one of claims 1 to 7, wherein the high-hardness resin is a polymethyl methacrylate resin.
9. The thermoforming laminate according to any one of claims 1 to 8, wherein the hard coat layer further contains nanoparticles, and the content of the nanoparticles is 0.1 to 6.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A).
10. The thermoforming laminate according to any one of claims 1 to 9, wherein the hard coat layer further contains a light stabilizer, and the amount of the light stabilizer is 0.1 to 4.0 parts by mass per 100 parts by mass of the urethane (meth)acrylate resin (A).
11. A thermoforming laminate according to any one of claims 1 to 10, wherein the surface of the hard coat layer has a protective film on the surface opposite to the lamination surface with the base material layer, and the surface of the base material layer has a protective film on the surface opposite to the lamination surface with the hard coat layer.
12. The thermoforming laminate according to any one of claims 1 to 11, wherein the water contact angle of the surface of the hard coat layer is 100° or more.
13. On the surface of the hard coat layer, Medigauze is applied at a rate of 500 gf / cm². ２ A thermoforming laminate according to any one of claims 1 to 12, which, when abraded by reciprocating under pressure, remains undamaged after 100 reciprocations.