JP6049071B2 - Polyester resin composition sheet - Google Patents

Description

The present invention relates to a polyester resin composition sheet. More specifically, the present invention relates to a polyester-based resin composition sheet that has stress crack resistance, impact resistance, weather resistance, surface hardness, and embossability at a high level and can be suitably used for a decorative sheet.

Traditionally, furniture such as display cabinets, storage cabinets, cupboards, desks, etc .; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, personal computers; or wood, plywood, laminated wood as building components such as floors, walls, bathrooms, etc. Used for decorative decorations by attaching a decorative sheet to the surface of a base material made of a wood-based material such as particle board or hard board; or on the surface of a base material made of a metal-based material such as iron or aluminum. ing. The decorative sheet is required to have a high level balance of not only decorativeness but also stress crack resistance, impact resistance, weather resistance, surface hardness, embossability and the like.

Amorphous polyester-based resin composition sheets have high transparency and gloss, and are excellent in embossability and impact resistance, and thus have been frequently used in such decorative sheets in recent years. However, the non-crystalline polyester resin composition sheet has a drawback that the stress crack resistance is not sufficient.

As a technique for solving this problem, the present applicant has proposed that (A) 50 to 99% by weight of a completely amorphous polyester resin, and conjugated diene rubber particles are graft-polymerized with methyl (meth) acrylate and vinyl aromatic. (B) a resin composition comprising 1 to 50% by weight of a graft copolymer, wherein (A) a completely amorphous polyester resin is terephthalic acid as a dicarboxylic acid component and ethylene glycol as a glycol component And 1,4-cyclohexanedimethanol, wherein the ethylene glycol is 60-80 mol% and 1,4-cyclohexanedimethanol is 20-40 mol% The composition ”further includes (E) a polyester-based resin whose crystallinity is infinitely close to 0 to 50%, specifically Is a glycol-modified polycyclohexylenedimethylene terephthalate (PCTG) composed of 100 mol% terephthalic acid, 42-32 mol% ethylene glycol and 58-68 mol% 1,4-cyclohexanedimethanol; 1-50 mol as a dicarboxylic acid component Acid-modified polycyclohexylenedimethylene terephthalate (PCTA) consisting of 1 to 25 mol% terephthalic acid, preferably 1 to 25 mol% isophthalic acid and 75 to 99 mol% terephthalic acid; etc. Is disclosed (Patent Document 1). However, this technology is “assumed to obtain stress crack resistance” as the main purpose, and as a decorative sheet, there are defects such as inferior embossability and heat laminating properties, so it is sufficiently satisfactory It wasn't.

Japanese Patent No. 3492318

An object of the present invention is to provide a polyester resin composition sheet that has a high level of stress crack resistance, impact resistance, weather resistance, surface hardness, and embossability, and can be suitably used for a decorative sheet. There is to do.

As a result of intensive studies, the present inventor has found that a sheet made of a resin composition containing an amorphous polyester resin having a specific composition is excellent in stress crack resistance and can achieve the above-described problems.

That is, the present invention
(A) A sheet (1) comprising a thermoplastic resin composition (P) containing 100 parts by mass of a polyester resin and (B) 1 to 10 parts by mass of a core-shell rubber,
The component (A) is
(A1) A terephthalic acid, isophthalic acid, ethylene glycol and neopentyl glycol as constituent monomers, and a total amount of monomer constituting 100 mol%, an amorphous polyester resin containing 90 mol% or more,
A sheet (1) comprising 70% by mass or more when the total amount of component (A) is 100% by mass.

The polyester resin composition sheet of the present invention has a high level of stress crack resistance, impact resistance, weather resistance, surface hardness, and embossability. Therefore, it can be suitably used for a decorative sheet.

Component (A) of the present invention is one or a mixture of two or more polyester resins, and (A1) terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol as constituent monomers, and 100 moles of all constituent monomers. %, The non-crystalline polyester resin contained in an amount of 90% by mole or more is contained in an amount of 70% by weight or more when the entire component (A) is 100% by weight. If it is less than 70% by mass, the embossability and weather resistance, or the stress crack resistance and pencil hardness are unsatisfactory. Preferably it is 75 mass% or more.

The component (A1) of the present invention is a non-crystalline polyester system comprising terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol as constituent monomers and an amount of 90 mol% or more when the total constituent monomers are 100 mol%. Resin. It has been common knowledge to those skilled in the art that a resin composition sheet containing a large amount of an amorphous polyester-based resin has insufficient stress crack resistance. Surprisingly, however, the present inventors have found that when the component (A1) of the present invention is used as an amorphous polyester-based resin, good stress crack resistance is exhibited. Moreover, since the component (A1) is non-crystalline, it has good transparency and gloss, and is excellent in embossability and impact resistance.

The component (A1) is preferably an amorphous polyester-based resin containing 95 mol% or more when terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol are used as constituent monomers and the total constituent monomers are 100 mol%. . More preferably, when the total constituting monomer is 100 mol%, terephthalic acid 30 to 45 mol%, isophthalic acid 5 to 20 mol%, ethylene glycol 35 to 48 mol%, neopentyl glycol 2 to 15 mol%, The total of terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol is a non-crystalline polyester resin having a concentration of 97 mol% or more.

Examples of monomer components other than terephthalic acid and isophthalic acid and ethylene glycol and neopentyl glycol that can be included in the component (A1) include polyvalent carboxylic acids such as orthophthalic acid and naphthalenedicarboxylic acid; diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol Polyhydric alcohols such as; aromatic dihydroxy compounds such as bisphenol A; and the like.

In the present specification, the copolymer composition of the polyester resin was determined using ¹ H-NMR. That is, an ECX400P type (trade name) nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used for measurement under the following conditions.
Measuring nucleus ¹ H (400 MHz)
Measurement mode Single pulse pulse width 45 ° (5.12 μs)
Number of points 16k
Measurement range -2.5 to 12.5ppm
Repeat time 7.8 seconds Accumulation count 64 times Measurement solvent Chloroform-d
Sample concentration 20mg / 0.6ml
Measurement temperature 23 ℃
Window function exponential (BF: 0.18Hz)
Internal standard for chemical shift chloroform (7.24ppm)

The attribution of the peak is “Polymer Analysis Handbook (First Edition, September 20, 2008, edited by Japan Analytical Chemistry Society, Polymer Analysis Research Meeting, Asakura Shoten Co., Ltd.), especially pages 496-503” and “ The copolymer composition was calculated from the peak area ratio by referring to the NMR database (http://polymer.nims.go.jp/NMR/) of the National Institute for Materials Science Material Information Station. Specifically, the structural unit derived from terephthalic acid is a hydrogen signal of an aromatic ring appearing near 8.05 ppm, and the structural unit derived from isophthalic acid is based on either the main chain of an aromatic ring appearing near 8.70 ppm. The position of the hydrogen signal, the ethylene glycol-derived structural unit is the main chain methylene hydrogen signal appearing near 4.65 ppm, and the neopentyl glycol-derived structural unit is the main chain methylene hydrogen appearing near 4.20 ppm. Signal was used.
The ¹ H-NMR analysis of the copolymer composition of the polyester resin can also be performed at Mitsui Chemical Analysis Center, Inc.

In this specification, a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. is used, and after holding the sample at 320 ° C. for 5 minutes, the sample is cooled to −50 ° C. at a temperature lowering rate of 20 ° C./min. A polyester having a heat of fusion of 10 J / g or less in a melting curve obtained by performing DSC measurement with a temperature program of heating to 320 ° C. at a heating rate of 20 ° C./min after holding at 5 ° C. for 5 minutes is non-crystalline. Defined.

The density measured by the underwater substitution method of ISO 1183 of component (A1) is preferably 1250 to 1400 Kg / m ³ . If it is less than 1250 Kg / m ³ , the stress crack resistance may be insufficient. If it exceeds 1400 Kg / m ³ , the impact resistance may be insufficient. More preferably, it is 1300-1360 Kg / m < ³ >.

As a commercial example of such an ingredient (A1), Sinopec of China Petrochemical Industry Chemical Fiber Co., Ltd. (China Petrochemical Industry &#20221; Co., Ltd.)
FG702 (product name) can be listed.

When the sheet (1) does not require transparency, specifically, when the thermoplastic resin composition (P) is colored with a concealing pigment, the stress crack resistance is further enhanced. The component (A) is preferably a mixture comprising the component (A1) and the (A2) polybutylene terephthalate resin. The upper limit of the amount of component (A2) is 30% by mass or less, where the total of component (A1) and component (A2) is 100% by mass. When it exceeds 30 mass%, embossing property will fall. More preferably, it is 25 mass% or less. On the other hand, there is no particular lower limit to the amount of component (A2), but it is preferably 1% by mass or more in order to obtain an effect of improving stress crack resistance. More preferably, it is 10 mass% or more.

Examples of commercially available components (A2) include Toraycon (trade name) manufactured by Toray Industries, Inc. and Novaduran (trade name) manufactured by Mitsubishi Engineering Plastics Corporation.

Component (B) of the present invention is a rubber having a core-shell structure, and functions to improve extensibility, secondary workability, and impact resistance. Specifically, methacrylate ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acrylate graft graft Examples thereof include a copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. As the component (B), one or a mixture of two or more of these core-shell rubbers can be used.

The compounding quantity of the component (A) and the component (B) in the said thermoplastic resin composition (P) is 1-10 mass parts of components (B) with respect to 100 mass parts of components (A). If the amount of component (B) is less than 1 part by mass, embossability and impact resistance will be insufficient. When the compounding amount of the component (B) exceeds 10 parts by mass, pencil hardness and transparency are lowered. Preferably it is 2-6 mass parts of a component (B).

Examples of such commercially available component (B) include Kane Ace (trade name) of Kaneka Corporation, and Metabrene (trade name) of Mitsubishi Rayon Co., Ltd.

The optional components that can be included in the thermoplastic resin composition (P) include thermoplastic resins other than the components (A1) and (A2) and the component (B); pigments, inorganic fillers, organic fillers, resin fillers, Examples include flame retardants; additives such as lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants. The compounding quantity of these arbitrary components is about 0.1-25 mass parts normally, when a component (A) is 100 mass parts.

The thermoplastic resin composition (P) can be obtained by a melt-kneading method using the above-described components using an arbitrary melt-kneader. Examples of the melt kneader include a batch kneader such as a pressure kneader and a mixer; an extrusion kneader such as a co-rotating twin screw extruder and a different direction rotating twin screw extruder; a calender roll kneader. These may be used in any combination. The obtained resin composition can be formed into a sheet (1) of the present invention after being pelletized by an arbitrary method, for example, using a calendar processing machine, or using an extruder and a T die. . Pelletization can be performed by methods such as hot cut, strand cut, and underwater cut. Alternatively, the melt-kneaded resin composition may be directly sent to a calendering machine or a T-die to be formed into a sheet (1). Any calendar processing machine can be used, for example, an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverted L type 4 roll, and a Z type roll. it can. Any extruder can be used, and examples thereof include a single-screw extruder, a same-direction rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. Any T-die can be used, and examples thereof include a manifold die, a fishtail die, and a coat hanger die.

A hard coat (3) can be laminated on at least one surface of the sheet (1) of the present invention with or without an anchor coat (2). By providing the hard coat (3), the scratch resistance can be enhanced. As the paint used for forming the hard coat (3), those having high transparency and high gloss are preferable from the viewpoint of design. Examples of such a hard coat forming coating material include an active energy ray-curable resin composition.

The active energy ray-curable resin composition can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. For example, (meth) acryloyl such as polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether (meth) acrylate Group-containing prepolymer or oligomer; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobonyl (meth ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, -Methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, and trimethylsiloxy (Meth) acryloyl group-containing monofunctional reactive monomers such as ethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) pro And (2) -bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane-containing (meth) acryloyl group-containing bifunctional reactive monomers; trimethylolpropane tri (meth) acrylate, trimethylolethanetri (Meth) acryloyl group-containing trifunctional reactive monomers such as (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and (meth) acrylic acid such as dipentaerythritol hexaacrylate ) A compound having two or more isocyanate groups (—N═C═O) in one molecule of one or more selected from acryloyl group-containing hexafunctional reactive monomers, or a resin having one or more of the above as constituent monomers And / or a composition comprising a photopolymerization initiator. I can make it.

In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, and a trimethylolpropane adduct of isophorone diisocyanate. Polyisocyanates such as methylolpropane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and block isocyanates of the above polyisocyanates A urethane cross-linking agent can be used. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- Benzophenone compounds such as benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone Anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkyls such as acetophenone dimethyl ketal Phenone compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. Can do. These can be used alone or in combination of two or more.

Particularly preferable as the active energy ray-curable resin composition,
(Α) The following formula (1):
(Where R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more,
(Β) a polyisocyanate having two or more isocyanate groups in one molecule, and (γ) a photopolymerization initiator,
Activity wherein the ratio (a / b) of the number of hydroxyl groups (a) of component (α) to the number of isocyanate groups (b) of component (β) is in the range of 0.5 to 1.2 An energy beam curable resin composition (Q) can be mentioned.

In the above formula, R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 The total number of groups is 3 or more, preferably 3 to 9, and more preferably 4. In the above formula (1), when the sum of the number of (meth) acryloyloxy groups in R1 and the number of (meth) acryloyloxy groups in R2 is 2 or less, the hard coat has scratch resistance, abrasion resistance and resistance. Poor pollution. R1 and R2 may be the same or different from each other, but R1 and R2 are preferably the same.

The component (α) functions to trap oxygen radicals. In general, when a (meth) acryloyloxy functional group-containing compound is cured by radical polymerization, the radical polymerizable compound is susceptible to polymerization inhibition by oxygen radicals in the air, and particularly on the surface of a hard coat, the curing reaction is caused by oxygen radicals. Become slow. If the irradiation time of the active energy ray is lengthened so that the surface is sufficiently cured, the speed of the production line is reduced, and since the influence of oxygen radicals is relatively small inside the hard coat, the curing reaction proceeds excessively and is brittle. Hard coat with inferior bending resistance. On the other hand, the active energy ray-curable resin composition (Q) is not inhibited by oxygen radicals because the component (α) has the specific structure of the above formula (1), and therefore has a high curing reaction rate, and A hard coat having excellent scratch resistance, abrasion resistance, contamination resistance and bending resistance can be obtained. Component (α) has an ethanolamine residue, and the hydrogen of the methylene group next to the nitrogen atom in the ethanolamine residue is extracted to generate radicals, which are thought to be bound and trapped by oxygen radicals. It is done.

The component (α) can be produced, for example, by reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) with ethanolamine at room temperature. This reaction is highly active at room temperature and does not require a catalyst. In order to prevent gelation, it is preferable to add a solvent or the like to lower the apparent concentration.
R1-O—C (═O) —CH═CH ₂
(3)
R2-O-C (= O ) -CH = CH 2
(4)
Here, R1 and R2 are as defined above.

In addition, when the component (α) is produced by the above method, many kinds of side reaction products are generated in addition to the target component (α) which is the main product. In the paint field, the component (α) is Usually, these by-products are used.

Examples of the compounds represented by the above formulas (3) and (4) include TPGDA (trade name) (tripropylene glycol diacrylate) and OTA 480 (trade name) (glycerin propoxytriacrylate) manufactured by Daicel-Cytec, And dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

The OTA480 is a compound having the following formula (5).

Particularly preferred as the component (α) is a compound having the following formula (2).

When the component (α) is a compound having the above formula (2), the resulting composition has good storage stability, and the resulting hard coat has bending resistance, three-dimensional formability, scratch resistance, Very good balance between wear and contamination resistance. Also, in general, in a production line for producing a laminate obtained by applying a paint to a base film, a separator is placed on a hard coat in order to prevent the laminates from blocking each other when the laminate is wound around a roll. However, when the component (α) is a compound of the above formula (2), the curing reaction is very fast, so there is an advantage that it is not necessary to use a separator.

As the component (β), compounds having two or more isocyanate groups in one molecule exemplified above can be used. Among these, those having three or more isocyanate groups in one molecule are preferable from the viewpoint of the bending resistance of the hard coat and the storage stability of the paint, and in particular, hexamethylene represented by the following formula (6) A diisocyanate trimer having an isocyanate ring structure, or a hexamethylene diisocyanate trimer represented by the following formula (7) and a trimethylolpropane adduct may be suitably used. . These have a structural feature in which isocyanate groups are present at positions away from each other at the tip of the hexamethylene chain. Therefore, the obtained hard coat is elastic and has excellent scratch resistance and abrasion resistance.

The resin composition is cured by a reaction between a hydroxyl group in the component (α) and an isocyanate group in the component (β). The resin composition of the present invention has a ratio (a / b) of the number of hydroxyl groups (a) of the component (α) to the number of isocyanate groups (b) of the component (β) (a / b) so that curing is sufficiently caused. It is in the range of 5-1.2, preferably 0.7-1.1. When the ratio is less than the lower limit, the resulting hard coat is inferior in bending resistance. When the ratio is larger than the upper limit, the resulting hard coat is poor in stain resistance against water-borne contaminants such as water-based magic.

In the present specification, the number of hydroxyl groups per unit amount of the component (α) was determined based on JIS-K-1557-1: 2007. That is, the hydroxyl group of component (α) is acetylated with an acetylating reagent (acetic anhydride in pyridine), then excess acetylating reagent is hydrolyzed with water, and the resulting acetic acid is titrated automatically by Kyoto Denshi Kogyo Co., Ltd. The above number was determined by titration with an ethanol solution of potassium hydroxide using an apparatus AT-610 type. Further, the number of isocyanate groups per unit amount of the component (β) was determined based on JIS-K-7301: 1995. That is, after reacting the isocyanate group of the component (β) with dinormal butylamine, the excess dinormal butylamine is titrated with an aqueous hydrochloric acid solution using a potentiometric automatic titrator AT-610 type of Kyoto Electronics Industry Co., Ltd. The above number was determined.

As the component (γ), the photopolymerization initiator described above can be used. The amount of the component (γ) can be appropriately selected depending on the type of other components and the desired coating thickness, and is generally 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (α). Degree.

In addition, the active energy ray-curable resin composition (Q) may include an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, if necessary. One or more additives such as a colorant, a leveling agent, a thixotropic agent, and a filler may be included.

Preferable optional components include fine particles having a particle diameter of 1 nm to 300 nm. The hardness of the hard coat (3) can be increased by using the fine particles in an amount of 1 to 50 parts by mass, preferably 3 to 25 parts by mass with respect to 100 parts by mass of the component (α).

As the fine particles, either inorganic fine particles or organic fine particles can be used.

Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal fine particles; metal sulfide fine particles; metal nitride fine particles; Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more.

In addition, for the purpose of increasing the dispersibility of the fine particles in the paint or increasing the hardness of the resulting coating film, the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Coupling agent; Organic compound having an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group and allyl group and reactive functional group such as epoxy group; Surface treatment agent such as fatty acid and fatty acid metal salt You may use what was processed.

Among these, in order to obtain a hard coat (3) with higher hardness, silica and aluminum oxide fine particles are preferable, and silica fine particles are more preferable. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

The particle diameter of the fine particles is preferably 300 nm or less in order to maintain the transparency of the hard coat (3). When the particle diameter is coarse, the effect of improving the hardness of the hard coat (3) may not be obtained. More preferably, it is 200 nm or less, More preferably, it is 120 nm or less. On the other hand, there is no particular lower limit of the particle diameter, but normally available particles are at most about 1 nm even if they are fine.

In the present specification, the particle diameter of the fine particles is a cumulative particle diameter distribution curve of 50 measured using a laser diffraction / scattering particle size analyzer MT3200II (trade name) manufactured by Nikkiso Co., Ltd. The particle diameter is mass%.

Moreover, since the said active energy ray curable resin composition (Q) is diluted to the density | concentration which is easy to apply, it may contain the solvent as needed. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. For example, known materials such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and diacetone alcohol can be used.

The active energy ray-curable resin composition (Q) can be obtained by mixing and stirring these components.

The thickness of the hard coat (3) is preferably 0.5 μm or more. If it is thinner than this, the effect of improving the scratch resistance may not be obtained. On the other hand, there is no particular upper limit on the thickness of the hard coat (3). However, since an unnecessarily thick hard coat only increases the cost, the thickness is 60 μm at most.

When the laminate of the present invention is provided with the hard coat (3), the anchor coat (2) is previously applied to the surface of the sheet (1) as a base material in order to increase the adhesive strength with the hard coat (3). It may be provided.

As an anchor coating agent for forming the anchor coat (2), it is well dissolved in known solvents such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetone and the like. As long as a sufficient anchor effect can be obtained, there is no particular limitation, and conventional ones such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used. Commercially available examples include Byron 24SS (trade name) manufactured by Toyobo Co., Ltd., AU2141NT (trade name) manufactured by Tokushi Co., Ltd., and the like.

When the anchor coat (2) is provided, the anchor coat agent (2) is formed by applying an anchor coat agent to the surface of the sheet (1) as a base material by a conventional method. ) Can be laminated with a hard coat (3).

The thickness of the anchor coat (2) is usually about 0.1 to 5 μm, preferably 0.5 to 2 μm.

The method for applying the paint or anchor coating agent for hard coating is not particularly limited, and a known web coating method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Method for measuring sheet physical properties (a) Stress crack resistance Procter &Gamble's orange oil-containing alkaline detergent “Meister Proper” (trade name) 20 ml of magic pen (red) ink 10 A test liquid was prepared by mixing at a drop ratio.
The sheet (1) was subjected to three-dimensional laminating using a membrane molding machine on a medium density fiber board (MDF) having a length of 150 mm, a width of 18 mm, and a thickness of 10 mm via an adhesive to obtain a test piece.
The test piece obtained above was first stored for 1 week in an environment of a temperature of 60 ° C. and a relative humidity of 95%.
Next, spread a Kimwipe (trade name) of Nippon Paper Crecia Co., Ltd. cut to a size of 30 mm × 40 mm on the surface of the test piece, and place 10 drops of the test solution obtained above using a dropper. Product name) was uniformly dropped onto the product. After dripping, the air bubbles between Kimwipe (trade name) and the test piece are removed using tweezers, and the Kimwipe (trade name) and the test piece are brought into close contact with each other in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Stored in. Every 24 hours of storage time, 10 drops of the above-mentioned test solution was dropped, and the operation was repeated for 72 hours while repeating the operation of removing bubbles and bringing them into close contact.
After a predetermined time has passed, remove the Kimwipe (trade name) containing the test solution on the test piece, wipe the test piece with water soaked with Kimwipe (trade name), and then wipe with a dry Kimwipe (trade name). Then, the test solution adhering to the surface of the test piece was completely removed.
Then, the crack which arose in the test piece was observed visually, and the following criteria evaluated.
◎: No cracks are observed ○: Only minor cracks are present ×: Cracks can be clearly recognized

(B) Pencil Hardness According to JIS K 5600-5-4, the surface hardness of the sheet (1) was evaluated using a pencil {"Uni" (trade name) of Mitsubishi Pencil Co., Ltd.} under the condition of 200 g load.

(C) Weather resistance (weather resistance discoloration)
Daipla-Wintesu Inc. metal halide lamp / KF-filter type accelerated weathering tester using "Daipla Metal Weather KU-R5N-A (trade name)", illuminance 70 mW / cm ^2, temperature of 53 ° C., 50% relative humidity After irradiating for 20 hours under the conditions, it was left to stand for 4 hours under conditions of a temperature of 30 ° C. and a relative humidity of 98%, and then a series of operations of spraying pure for 10 seconds was taken as one cycle, and two cycles of treatment were performed. It was.
The color difference (ΔE * ab) between the untreated specimen and the treated specimen was measured using a spectrocolorimeter “CM-600d (trade name)” manufactured by Konica Minolta Optics.

Sheet workability (d) embossing sheet (1) was passed through the embossing machine, it was preheated sandwiched between the preheat roll and the pressing roll set at a temperature 120 ° C., as it is continuously the temperature Embossing was performed by sandwiching the embossing roll set at 150 ° C. and a smooth roll having a rubber surface so that the surface on the preheating roll side was on the embossing roll side. As the embossing machine, a preheating roll and a machine equipped with a wood embossing roll BR-16 with wood grain conduit and satin plating are used, and the pressure is 5 kgf / cm ^2.
The line speed was 3 m / min. In the above processing conditions, if little or no embossing is formed, or if the sheet has cracks or holes, the temperature of the preheating roll is in the range of 100 to 180 ° C., and the temperature of the embossing roll is 120 to It adjusted suitably in the range of 200 degreeC. Workability was visually evaluated according to the following criteria.
○: At least under the optimum conditions, the emboss is formed over the entire sheet surface, and there is no cracking or perforation of the sheet.
X: Little or no embossing is formed even under optimum conditions, or there are cracks and holes in the sheet.

Raw material used (A1) Amorphous polyester resin (A1-1) containing terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol as constituent monomers and 90 mol% or more when the total constituent monomers are 100 mol% Sinopec of China Petrochemical Industry Chemical Fiber Co., Ltd.
FG702 (trade name):
The monomer composition is 39.0 mol% terephthalic acid, 10.2 mol% isophthalic acid, 42.6 mol% ethylene glycol, 7.1 mol% neopentyl glycol, 0.6 mol% diethylene glycol and 0.5 mol% bisphenol A. No melting peak due to complete non-crystallinity (melting heat 0 J / g). Density 1330Kg / m ³

(A2) Polybutylene terephthalate resin (A2-1) Toraycon 1200M (trade name) manufactured by Toray Industries, Inc .:
The monomer composition is 50 mol% terephthalic acid and 50 mol% 1,4-butanediol. Heat of fusion 54 J / g. Density 1310 Kg / m ³ .

(A3) Other polyester resins (A3-1) KODAR PETG 6763 (trade name) manufactured by Eastman Chemical Company:
The monomer composition is 50 mol% terephthalic acid, 35 mol% ethylene glycol and 15 mol% 1,4-cyclohexanedimethanol. No melting peak due to complete non-crystallinity (melting heat 0 J / g). Density 1270 Kg / m ³ .
(A3-2) Easter Chemical Co., Ltd. EASTER PCTG 5445 (trade name):
The monomer composition is 50 mol% terephthalic acid, 18 mol% ethylene glycol and 32 mol% 1,4-cyclohexanedimethanol. Heat of fusion 11 J / g. Density 1230 Kg / m ³ .
(A3-3) THERMX PCTA 6761 (trade name) of Eastman Chemical Company:
The monomer composition is 40 mol% terephthalic acid, 10 mol% isophthalic acid and 50 mol% 1,4-cyclohexanedimethanol. Heat of fusion 23 J / g. Density 1215 Kg / m ³ .

(B) Core shell rubber (B-1) Kaneka FM-40 (trade name) of Kaneka Corporation:
Methacrylic acid ester / acrylonitrile / butyl acrylate graft copolymer.

Example 1
100 parts by mass of the above (A1-1), 2 parts by mass of the above (B-1), 0.5 parts by mass of the lubricant “Roxyol G78 (trade name)” of Cognis Japan, and titanium oxide of Ishihara Sangyo Co., Ltd. A white resin sheet having a thickness of 250 μm was obtained by a T-die extrusion film forming method using a polyester resin composition with 12 parts by mass of “White Pigment CR-60-2 (trade name)”. The test of said (i)-(d) was done about the obtained sheet | seat. The results are shown in Table 1.

Examples 2-5, Comparative Examples 1-8
The same procedure as in Example 1 was performed except that the polyester resin composition used was changed to the formulation shown in Table 1. The results are shown in Table 1 for Examples 2 and 3 and Comparative Examples 1 to 4. The results are shown in Table 2 for Examples 4 and 5 and Comparative Examples 5 to 8.

Example 6
A transparent resin sheet was obtained in the same manner as in Example 1 except that Ishihara Sangyo Co., Ltd.'s titanium oxide (white pigment) “Typaque CR-60-2 (trade name)” was not used. The results are shown in Table 2. JIS K
The haze value measured according to 7105 was 2.7%.

Comparative Example 9
A transparent resin sheet was obtained in the same manner as in Comparative Example 1 except that Ishihara Sangyo Co., Ltd. titanium oxide (white pigment) “Typaque CR-60-2 (trade name)” was not used. The results are shown in Table 2. JIS K
The haze value measured according to 7105 was 2.7%.

Synthesis of component (α-1) OTA480 (product name, glycerin propoxytriacrylate of the above formula (5)) and 2-aminoethanol manufactured by Daicel Cytec Co., Ltd. and 1 mol of the latter with respect to 2 mol of the former In a glass beaker at a temperature of 23 ° C. and allowed to react at a temperature of 23 ° C. for 72 hours to form an ethanolamine-modified polyether acrylate having a structure of the above formula (2) and having four acryloyloxy groups (α-1 ) The number of hydroxyl groups per unit amount of the component (α-1) was 1.09 mol / kg as measured by the method described above.

Active energy ray-curable resin composition (Q) for hard coat (3)
100 parts by mass of component (α-1) as component (α) and 25 parts by mass of Coronate HX (trade name, polyisocyanate of formula (6) above) manufactured by Nippon Polyurethane Industry Co., Ltd. as component (β) 7 parts by mass of benzophenone (γ-1) as the component (γ), 8 parts by mass of high-purity colloidal silica having an average particle diameter of 80 nm as the other component, and 200 parts by mass of 1-methoxy-2-propanol as the diluent solvent The active energy ray-curable resin composition (Q) was obtained by stirring.
The number of isocyanate groups per unit amount of component (β-1) was 5.12 mol / kg as measured by the method described above. Therefore, the ratio (a / b) is (1.09 × 100) / (5.12 × 25) = 0.85.

Example 7
Applying the active energy ray-curable resin composition (Q) obtained above to the surface of the sheet obtained in Example 1 above, drying, irradiating with ultraviolet rays, and winding the obtained laminate on a roll It was carried out continuously at a line speed of 50 m / min in a series of production lines. The roll could be wound well without using a separator. The resin composition was applied using a film Mayer bar type coating apparatus so that the hard coat thickness after drying was 11 μm. In addition, the line speed in Table 3 and Table 4 is the fastest speed which can manufacture a laminated body stably in a production line. The obtained laminates were subjected to the following tests (1) to (7). The results are shown in Table 3.

Example 8
Sumidur HT (β-2) of Sumika Bayer Urethane Co., Ltd. (trade name, polyisocyanate of formula (7) above, isocyanate per unit amount as component (β) of active energy ray-curable resin composition (Q) The number of groups: 3.10 mol / kg) The same procedure as in Example 7 was carried out except that (B-2) was used in an amount of 42 parts by mass. The results are shown in Table 3.

Examples 9-14
The same procedure as in Example 5 was performed except that the amount of the component (β-1) of the active energy ray-curable resin composition (Q) was changed as shown in Table 2. Examples 9 to 13 show the results in Table 3. Example 14 shows the results in Table 4.

Synthesis of component (α-2) In the synthesis of the above component (α-1), tripropylene glycol diacrylate (manufactured by Daicel-Cytec) was used instead of OTA480 (manufactured by Daicel-Cytech, Inc., trade name). The ethanolamine-modified polyether acrylate (α-2) having two acryloyloxy groups was synthesized in the same manner as in the synthesis of the component (α-1) except that was used. The number of hydroxyl groups per unit amount of the component (α-2) was 1.51 mol / kg.

Example 15
In Example 12, it carried out similarly to Example 12 except having used the component ((alpha) -2) as a component ((alpha)) of active energy ray curable resin composition (Q). The line speed at this time was 50 m / min as in Example 12, but a separator was required for winding on the roll. The results are shown in Table 4.

Example 16
In Example 7, as component (α) of the active energy ray-curable resin composition (Q), tripropylene glycol diacrylate (manufactured by Daicel-Cytec Corp., number of hydroxyl groups per unit amount: 0 mol / kg) (α -3), and an alkylphenone photopolymerization initiator (Darocur 1173 (trade name) of Ciba Japan Co., Ltd., 2-hydroxy-2-methyl-1-phenyl-propane-1- On) (γ-2) was carried out in the same manner as in Example 7 except that it was used in an amount of 5 parts by mass. The line speed at this time was 30 m / min. The reason why benzophenone (γ-1) was not used as the component (γ) is that when the component (α) is the above (α-3), the curing rate is slow in the above (γ-1). The (γ-2) was used as the component (γ) so that the curing of the (α-3) and the (β-1) proceeded at a high speed without gelation. The same applies to Examples 17 and 18 below. The amount of the component (γ) is 5 parts by mass because 7 parts by mass is too large and gelation occurs. The results are shown in Table 4.

Example 17
In Example 16, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.63 mol / kg) (α-4) was used as the component (α), and the ratio a The same procedure as in Example 16 was performed except that the amount of (β-1) was adjusted so that / b was 0.85, which was the same as in Example 7. The results are shown in Table 4. In addition, the above (α-4) does not have a hydroxyl group in terms of structure, but a hydroxyl group exists because a part of the acryloyloxy group is hydrolyzed. The same applies to (α-5) in Example 18 below.

Example 18
In Example 16, ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., number of hydroxyl groups per unit amount: 0.35 mol / kg) (α-5) was used as the component (α), and the ratio a The same procedure as in Example 16 was performed except that the amount of (β-1) was adjusted so that / b was 0.85, which was the same as in Example 7. The results are shown in Table 4.

Example 19
In Example 7, it carried out similarly to Example 7 except not having used the high purity colloidal silica with an average particle diameter of 80 nm as other components of active energy ray curable resin composition (Q). The results are shown in Table 4.

Test method of laminate physical properties (1) The hard coat surface of the laminate was measured according to 60 ° gloss JIS-7105-1981.

(2) Pencil hardness In accordance with JIS K 5600-5-4, the hardness of the hard coat surface of the laminate was evaluated using a pencil {"Uni" (trade name) of Mitsubishi Pencil Co., Ltd.} under the condition of 200 g load. .

(3) Scratch resistance-1
The laminate obtained above was cut into a size of 200 mm in length and 25 mm in width to obtain a test piece, which was placed on a JIS L 0849 Gakushin tester so that the hard coat surface was the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin Tester, a load of 1 kg was placed, and the surface of the test piece was rubbed 5 times. The surface was visually observed and evaluated according to the following criteria.
◎: No scratch ○: There are 1 to 3 scratches Δ: There are 4 to 10 scratches ×: There are 11 or more scratches

(4) Scratch resistance-2
The laminate obtained above was cut into a size of 150 mm long × 75 mm wide to obtain a test piece, which was placed on a glass plate so that the hard coat surface was the surface. Using a four-row brass brush (load: 500 gf) manufactured by Nakaya Brush Industry, the surface of the test piece was rubbed 10 times at a distance of 100 mm in one way. The surface was visually observed and evaluated according to the following criteria.
◎: No scratch ○: There are 1 to 3 scratches Δ: There are 4 to 10 scratches ×: There are 11 or more scratches

(5) Stain resistance-1
The hard coat surface of the laminate obtained above was spot-contaminated with oily red magic, and then the contaminated portion was covered with a watch glass and left at room temperature for 24 hours. Next, using a Kimwipe (trade name) sufficiently containing isopropyl alcohol, the contaminated part was cleaned by wiping until the Kimwipe (trade name) was not newly soiled. Evaluated by criteria.
◎: No contamination ○: Slight contamination remains △: Contamination remains significantly ×: Contamination remains significantly

(6) Pollution resistance-2
The hard coat surface of the laminate obtained above was spot-contaminated with aqueous red magic, and then the contaminated part was covered with a watch glass and left at room temperature for 24 hours. Next, after thoroughly washing the contaminated part with running water, using a Kimwipe (trade name) sufficiently soaked in tap water, wiping until the Kimwipe (trade name) is no longer soiled and washed, Were visually observed and evaluated according to the following criteria.
◎: No contamination ○: Slight contamination remains △: Contamination remains significantly ×: Contamination remains significantly

(7) Bending resistance The laminate obtained above was cut into a size of 100 mm × 50 mm, and this was cut into a double-sided tape No. 2 manufactured by Nitto Denko Corporation. Using 500 A, a test piece was prepared by adhering to an aluminum plate having a thickness of 0.3 mm so that the coating film surface was the surface. Using a JIS K 5600-5-1 type 1 bending test apparatus to which a mandrel having a diameter of 2 mm is attached, the test piece is turned to 180 ° at an even speed over 2 seconds so that the hard coat surface is on the outside. Bent. After the end of the bending, the presence or absence of cracks in the hard coat was confirmed for the central 30 mm portion of the bent portion, and evaluated according to the following criteria.
◎: No crack ○: One crack Δ: Two to three cracks ×: Four or more cracks

The aspect (Examples 1-5) colored white of the polyester-type resin composition sheet | seat of this invention is excellent in stress crack resistance, pencil hardness, a weather resistance, and its embossing property is also favorable. On the other hand, Comparative Examples 1 to 6 that do not contain a predetermined amount of component (A1) are inferior in at least one of stress crack resistance, pencil hardness, weather resistance, and embossability. Moreover, the comparative example 7 containing more than a predetermined amount of component (B) has low pencil hardness, and the comparative example 8 of less than predetermined amount is inferior to embossing property.

The transparent aspect (Example 6) of the polyester-type resin composition sheet | seat of this invention is excellent in stress crack resistance, pencil hardness, transparency, and its embossing property is also favorable. Furthermore, the weather resistance is also superior to that of Comparative Example 9. On the other hand, the comparative example 9 which does not contain a component (A1) is inferior to stress crack resistance and pencil hardness.

Moreover, in the laminated body of the present invention, in embodiments (Examples 6 to 11 and 18) in which a specific hard coat is employed, a laminated body having excellent gloss, pencil hardness, scratch resistance, stain resistance, and bending resistance is obtained. Can be provided.

Claims (4)

(A) A sheet (1) comprising a thermoplastic resin composition (P) containing 100 parts by mass of a polyester resin and (B) 1 to 10 parts by mass of a core-shell rubber,
The component (A) is
(A1) Amorphous polyester resin 70 to 99% by mass containing 90% by mol or more of terephthalic acid and isophthalic acid as well as ethylene glycol and neopentyl glycol when the total monomer content is 100% by mol. When
(A2) Polybutylene terephthalate resin 30-1% by mass,
Here, the sheet (1) where the sum of the component (A1) and the component (A2) is 100% by mass .
When the component (A1) is 100 mol% of all the constituent monomers,
Including 30-45 mol% terephthalic acid, 5-20 mol% isophthalic acid, 35-48 mol% ethylene glycol, 2-15 mol% neopentyl glycol, and
The sheet (1) according to claim 1, wherein the total amount of terephthalic acid and isophthalic acid, ethylene glycol and neopentyl glycol is 97 mol% or more, which is an amorphous polyester resin.
A laminate comprising a hard coat (3) laminated on at least one surface of the sheet (1) according to claim 1 or 2 with or without an anchor coat (2).
The hard coat (3)
(Α) The following formula (1):
(Where R1 and R2 are each a polyether (meth) acrylate residue having one or more (meth) acryloyloxy groups, and the number of (meth) acryloyloxy groups in R1 and (meth) acryloyloxy in R2 Ethanolamine-modified polyether (meth) acrylate having a total number of groups of 3 or more,
(Β) a polyisocyanate having two or more isocyanate groups in one molecule, and (γ) a photopolymerization initiator,
Active energy ray-curable resin in which the ratio (a / b) of the number of hydroxyl groups (a) of component (α) to the number of isocyanate groups (b) of component (β) is in the range of 0.5 to 1.2 The laminate according to claim 3, wherein the laminate is formed by curing a paint containing the composition (Q).