JP2004091795A - Resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin sheet suitable for membrane press molding, vacuum press molding, air pressure press molding and the like. <P>SOLUTION: The resin sheet is obtained by adding a lubricant into a composition comprising (A) 50-99.9 wt.% wholly noncrystalline polyester resin and (D) 0.1-50 wt.% thermoplastic polyester elastomer and forming the obtained molding material, wherein the lubricant is one or more selected from hydrocarbon lubricants, fatty acid lubricants, aliphatic alcohol lubricants, aliphatic amide lubricants, aliphatic ester lubricants and aliphatic metallic soap lubricants. The resin sheet has excellent properties such as workability, formability, impact resistance and transparency and hardly causes plate out and is hardly whitened when embossing or thermal laminating. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a resin sheet.

BACKGROUND ART Conventionally, laminated decorative sheets have been widely used by being bonded to metal or wood-based materials such as furniture, cabinets, fittings, desks, cupboards, and the like.
Further, the laminated decorative sheet is used as a single sheet or as a laminated decorative sheet in which a sheet is laminated on an upper ground, a ground, and a middle ground and a plurality of sheets.
In addition, a laminated decorative sheet is subjected to membrane press molding on an adherend having a complicated curved surface, and is adhered to the contour thereof.

Such a conventional laminated decorative sheet includes, for example, a sheet described in Patent Literature 1. This is a laminated decorative sheet comprising a base layer of an opaque polyolefin resin film and an amorphous polyethylene terephthalate resin film.
The amorphous polyethylene terephthalate resin film used for the sheet described in Patent Document 1 has a partial crystallinity, although it is called “amorphous”.

Patent Document 2 describes a hard shrink film. This comprises an amorphous polyester resin component, at least one polymer block component mainly composed of a vinyl aromatic hydrocarbon, and at least one polymer block mainly composed of a conjugated diene derivative. And a polymer component comprising the vinyl aromatic hydrocarbon.
According to this conventional technique, a laminated decorative sheet and a hard shrinkable film having excellent moldability and excellent impact resistance are obtained.

Furthermore, Patent Document 3 describes an impact modifier for a polyalkylene terephthalate resin. A resin composition comprising a polyalkylene terephthalate resin such as polybutylene terephthalate and polyethylene terephthalate, and a core-shell polymer having a rubber elastic body as a core and a glassy polymer as a shell.

According to this prior art, a resin composition having excellent impact resistance can be obtained.

JP-A-7-24979 JP-A-62-124928 JP-A-2-129266

However, the conventional resin composition and the laminated decorative sheet have a problem that a whitening phenomenon occurs at the time of embossing, thermal bonding, and bending at the time of secondary processing, and transparency is poor. Further, there is a problem that plate-out occurs during roll molding (calender molding, embossing molding) or injection molding.
Conventionally, in addition to a transparent resin sheet, a resin sheet having a colored or printed base has been widely used. In this case, in order to give a deeper design, the upper layer is generally made of a transparent sheet. However, its design has not yet reached a sufficient level. On the other hand, a resin sheet using such a colored or printed sheet as a single layer or as an upper layer has a problem in that it tends to whiten when being bent, resulting in poor workability.

The object of the present invention is excellent in workability, moldability, physical properties such as impact resistance, excellent in transparency, hardly plate out, and hardly whitened at the time of embossing or heat bonding, especially membrane press molding, An object of the present invention is to provide a resin composition and a resin sheet suitable for vacuum press molding, pressurized air press molding, and the like.

In addition, the membrane press molding is to heat a thermoplastic decorative sheet having a desired thickness or a desired coloring or surface printing to a temperature close to its softening point, and apply the heated sheet to an adherend having a predetermined shape, such as a door of a kitchen set. Over an adherend with a complex curved surface such as above, and further overlaid with a stretchable membrane (film-like material), for example, a rubber film. A decorative sheet is attached to the surface.
In addition, vacuum press molding and pressurized air press molding have the same basic principle as membrane press molding, but the former is a method of molding by vacuum pressure without using membrane press rubber, and the latter uses air pressurization. It is a molding method.

As a result of intensive studies, the present inventors have been able to solve the above-mentioned conventional problems.
The invention of claim 1 provides a composition comprising (A) 50 to 99.9% by weight of a completely amorphous polyester resin and (D) 0.1 to 50% by weight of a thermoplastic polyester elastomer, further comprising a hydrocarbon-based resin. One or more lubricants selected from lubricants, fatty acid lubricants, aliphatic alcohol lubricants, aliphatic amide lubricants, aliphatic ester lubricants and aliphatic metal soap lubricants are added, and the resulting molding material is molded. It is a resin sheet obtained by:
The invention according to claim 2 is the resin sheet according to claim 1, wherein the resin sheet is colored and / or printed on the surface.
The invention of claim 3 is a laminated resin sheet obtained by laminating two or more layers of the sheet of claim 1.
The invention of claim 4 is a laminated resin sheet obtained by laminating two or more layers of the sheet of claim 2.
The invention according to claim 5 is a laminated resin sheet obtained by using the resin sheet according to claim 1 as an upper ground, using the resin sheet according to claim 2 as a base, and laminating both.
The invention of claim 6 is a laminated resin sheet obtained by using the resin sheet of claim 1 or 2 as an upper ground, using a thermoplastic resin sheet as a base, and laminating both.
According to a seventh aspect of the present invention, the resin sheet according to the first aspect is used as an upper layer, and (A) 50 to 99% by weight of a completely amorphous polyester resin is used as an underlayer having a colored and / or printed surface. (B) graft copolymer and / or acrylic rubber particles obtained by graft-polymerizing (meth) acrylic ester and vinyl aromatic on conjugated diene rubber particles; This is a laminated resin sheet obtained by using a sheet composed of 1 to 50% by weight of the graft copolymer (C) obtained by graft polymerization and laminating both.
The invention according to claim 8 is the laminated resin sheet according to claim 7, wherein the resin sheet according to claim 2 is used as an upper ground.

According to the present invention, workability, moldability, excellent physical properties such as impact resistance, excellent transparency, almost no plate out, and hardly whitened at the time of embossing or heat bonding, especially membrane press molding, A resin sheet suitable for vacuum press molding, compressed air press molding, and the like is provided.

Component (A) (perfectly amorphous polyester resin)
The completely amorphous polyester resin (A) used in the present invention does not cause a decrease in physical properties due to recrystallization even when subjected to heat treatment again, and has no crystalline component. The crystallinity in the present invention means the crystallinity measured by the DSC method (JIS K7121).

(A) As the completely amorphous polyester-based resin, for example, a resin produced by a polycondensation reaction via an esterification reaction with terephthalic acid or dimethyl terephthalic acid as main components and ethylene glycol is preferably used.

The (A) completely amorphous polyester resin also includes a copolymer type obtained by copolymerizing a third component, in addition to the above-mentioned dicarboxylic acid and glycol components, and this type is preferable in the present invention. .

In a preferred embodiment of the present invention, as the third component, 1,4-cyclohexanedimethanol, terephthalic acid, isophthalic acid, or the like is suitable, and more preferably, the glycol component is composed of two or more types. Yes, and most preferably, the dicarboxylic acid component is terephthalic acid and the diol component is 50-99 mol% ethylene glycol and 1-50 mol% 1,4-cyclohexanedimethanol. In particular, it is preferable that the dicarboxylic acid component is terephthalic acid, and that the ethylene glycol is 60 to 80 mol% and the 1,4-cyclohexanedimethanol is 20 to 40 mol%.

粘度 The viscosity of the component (A) is preferably from 0.65 to 0.85 as an IV value.

A method for producing a completely amorphous polyester resin is already widely known in the art, and is disclosed in, for example, US Pat. No. 5,340,907.

The resin composition of the present invention comprises a graft copolymer (B) obtained by graft polymerizing (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles on a completely amorphous polyester resin component (A). A compound or a (C) graft copolymer obtained by graft-polymerizing (meth) acrylic acid ester on acrylic rubber particles to the completely amorphous polyester resin component (A) Alternatively, it can be obtained by blending the (B) graft copolymer and (C) with the completely amorphous polyester resin component (A). That is, the resin composition of the present invention can use two types of graft copolymers. Hereinafter, both graft copolymers will be described.

(B) Graft copolymer (B) The graft copolymer is obtained by graft-polymerizing a conjugated diene rubber particle with a (meth) acrylate and a vinyl aromatic.
The conjugated diene used for preparing the conjugated diene rubber particles is an olefin having a conjugated double bond, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1, Examples thereof include 3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

The preparation of the conjugated diene rubber particles is performed by polymerizing the conjugated diene as described above, but may be further copolymerized using vinyl aromatic or another copolymerizable monomer. Examples of the vinyl aromatic for this purpose include styrene, α-methylstyrene, α-ethylstyrene, and their nuclear-substituted derivatives such as vinyltoluene, isopropenyltoluene, chlorostyrene, and aromatic vinylidene. Examples of other copolymerizable monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; vinyl cyanide such as acrylonitrile and methacrylonitrile; and vinylidene cyanide.

Furthermore, crosslinking may be carried out using a crosslinking agent. Examples of the crosslinking monomer include monomers having two or more reactive double bonds, for example, aromatic divinyl monomers such as divinylbenzene; ethylene glycol di (meth) acrylate, butylene glycol Alkane polyol polyacrylates such as (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate; However, butylene glycol diacrylate and hexanediol diacrylate are particularly preferably used.

The conjugated diene rubber particles preferably comprise 1 to 65% by weight of a conjugated diene, 0 to 35% by weight of a vinyl aromatic, and 0 to 35% by weight of another copolymerizable monomer. The crosslinking agent is used in a small amount, and a specific amount is appropriately selected.

重合 The polymerization of the conjugated diene rubber particles can be carried out by a known polymerization means, and is not particularly limited.

The obtained conjugated diene rubber particles preferably have a particle diameter of 0.05 to 1.0 µm. More preferably, the thickness is 0.05 to 0.5 μm.

Next, the graft copolymer (B) is prepared by graft-polymerizing (meth) acrylate and vinyl aromatic onto the conjugated diene rubber particles. As the (meth) acrylate, those having 1 to 8 carbon atoms are preferable, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. These can be used together. Among them, methyl (meth) acrylate is desirable. As the vinyl aromatic, those exemplified above can be used.

In the case of graft polymerization of (meth) acrylic acid ester and vinyl aromatic, copolymerization can be performed using other components, that is, other copolymerizable monomers, crosslinking agents, and the like, if necessary. . As the other copolymerizable monomer and crosslinking agent, those exemplified above can be used. However, it is desirable to use these other components in a proportion of less than 50% by weight based on the total weight of the (meth) acrylate, vinyl aromatic and other components.

The copolymerization reaction between the conjugated diene-based rubber particles and the (meth) acrylic acid ester, vinyl aromatic, and other components used as necessary can use a known method, and is not particularly limited. For example, a seed emulsion polymerization method and the like can be mentioned.
(B) The proportion of the conjugated diene rubber component in the graft copolymer is preferably from 40 to 90% by weight.

(C) Graft copolymer The (C) graft copolymer is obtained by graft-polymerizing (meth) acrylic acid ester and vinyl aromatic on acrylic rubber particles.
Acrylic rubber particles are obtained by polymerizing an acrylate ester. As the acrylate, those having 2 to 8 carbon atoms in the alcohol component are suitable, and examples thereof include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate.

(4) The preparation of the acrylic rubber particles is carried out by polymerizing the acrylate ester described above, but may be further copolymerized using vinyl aromatic or other copolymerizable monomers. Alternatively, crosslinking may be performed using a crosslinking agent. Examples of these vinyl aromatics, other copolymerizable monomers, and cross-linking agents are those described in the section of the above (B) graft copolymer.

The acrylic rubber particles preferably comprise 1 to 65% by weight of an acrylate ester, 0 to 35% by weight of a vinyl aromatic, and 0 to 35% by weight of another copolymerizable monomer. The crosslinking agent is used in a small amount, and a specific amount is appropriately selected.

重合 The polymerization of the acrylic rubber particles can be performed by a known polymerization means, and is not particularly limited.

ア ク リ ル The obtained acrylic rubber particles preferably have a particle diameter of 0.05 to 1.0 µm. More preferably, the thickness is 0.05 to 0.5 μm.

Next, (C) a graft copolymer is prepared by graft-polymerizing (meth) acrylic acid ester and vinyl aromatic to the acrylic rubber particles. As the (meth) acrylic acid ester, those having 1 to 8 carbon atoms are preferable, and those described in the section of the above (B) graft copolymer are exemplified. As the vinyl aromatic, those described in the section of the above (B) graft copolymer are exemplified.

At the time of graft polymerization of (meth) acrylic acid ester, if necessary, other components, that is, another copolymerizable monomer, a cross-linking agent or the like may be used for copolymerization. As the other copolymerizable monomer and crosslinking agent, those exemplified above can be used. However, it is desirable to use these other components in a proportion of less than 50% by weight based on the total weight of the (meth) acrylate and the other components.

The copolymerization reaction between the acrylic rubber particles and the (meth) acrylic acid ester, vinyl aromatic, and other components used as necessary can use a known method, and is not particularly limited. For example, a seed emulsion polymerization method and the like can be mentioned.

割 合 The proportion of the acrylic rubber component in the (C) graft copolymer is preferably from 40 to 90% by weight.

The (B) graft copolymer and (C) graft copolymer preferably have a glass transition temperature of the graft component of 40 ° C. or higher.

The mixing ratio of the resin composition of the present invention is (A) 50 to 99% by weight of a completely amorphous polyester resin and (B) 1 to 50% by weight of a graft copolymer, preferably (A) completely amorphous polyester. 55 to 92% by weight of the base resin and 8 to 45% by weight of the (B) graft copolymer are preferred.

When (C) the graft copolymer is used, (A) 50 to 99% by weight of the completely amorphous polyester resin and (C) 1 to 50% by weight of the graft copolymer, preferably (A) completely non-crystalline polyester resin 55 to 92% by weight of the crystalline polyester resin and 8 to 45% by weight of the (C) graft copolymer are preferred.

Further, when (B) the graft copolymer and (C) are used in combination, (A) 50 to 98% by weight of a completely amorphous polyester resin, (B) 1 to 49% by weight of the graft copolymer and (C) The amount of the graft copolymer is preferably 1 to 49% by weight. However, the total of the components (A), (B) and (C) is 100% by weight.

The present invention also provides a resin sheet obtained by molding a composition containing (A) 50 to 99.9% by weight of a completely amorphous polyester resin and (D) 0.1 to 50% by weight of a thermoplastic polyester elastomer. Is provided.
As the thermoplastic polyester-based elastomer (D), for example, the following general formula (1) or (2) is preferable.

A terephthalic acid-based crystalline polyester hard segment (polybutylene terephthalate (PBT) or polybutylene naphthalate (PBN)) represented by the following general formula (3):

(Wherein, x represents an integer of 2 to 4, and p represents an integer of 8 to 140) Aliphatic polyether soft segment having a molecular weight of 600 to 6000 (polytetramethylene diglycol (PTMG), polypropylene) Glycol (PPG), polyethylene glycol (PEG)) and a segment copolyester having a molecular weight of 5,000 to 100,000.

(D) By setting the molecular weight of the thermoplastic polyester-based elastomer in the above range, the physical properties such as impact resistance, tensile strength, and cold resistance of the obtained resin sheet, and the moldability are further improved.

所 望 By appropriately selecting the molar ratio between the hard segment and the soft segment, desired physical properties of the resin sheet of the present invention, for example, impact resistance can be imparted.

For example, the molar ratio of the hard segment / soft segment is preferably 50 mol% or more for the soft segment.

The hard component is an aromatic polyester and the soft component is an aliphatic polyester, the hard component is an aromatic polyester and the soft component is an aliphatic polyester (for example, an aliphatic lactone elastomer), and the hard component is polybutylene. Examples thereof include (co) polymers in which the soft component is phthalate and the aliphatic component is an aliphatic polyether.

配合 The compounding amount of the component (A) and the component (D) is 50 to 99.9% by weight of the component (A) and 0.1 to 50% by weight, preferably 0.5 to 30% by weight of the component (D). More preferably, the component (D) is 1 to 30% by weight.

(4) If the component (D) is less than 0.1% by weight, the mechanical strength is poor.

The composition obtained by blending the components (A) and (D) can be formed into a sheet by the means described below, and is formed into a single-layer resin sheet (hereinafter, referred to as a transparent resin sheet). Can be used. The transparent resin sheet thus obtained is excellent in mechanical strength and transparency, hardly whitens during bending, and excellent in design. The transparent resin sheet can be colored by known means, and / or may be printed on the surface.

As one embodiment of the laminated resin sheet of the present invention, a laminated resin sheet obtained by laminating two or more transparent resin sheets, a laminated resin obtained by laminating two or more colored and / or surface-printed resin sheets are laminated. Examples of the sheet include those using the above-described colored and / or surface-printed resin sheet as a base and a transparent resin sheet as an upper base. In this case, it is needless to say that various types of grounds can be applied as needed, and this aspect is also included in the scope of the present invention.

別 に Alternatively, the laminated resin sheet of the present invention can use, as a base, a sheet made of the following (F) thermoplastic resin.

As the thermoplastic resin (F) used in the present invention, polyvinyl chloride, polyolefin (polyethylene, polypropylene, propylene-ethylene copolymer), (meth) acrylate, polycarbonate, polystyrene, AS-based resins, ABS-based resins, polyester-based resins, polyurethane-based, polyamide-based and the like are generally mentioned. This component (F) can also be processed into a sheet by means described below. When the component (F) is used as a base, the upper layer is preferably the above-mentioned transparent resin sheet or a resin sheet having a colored and / or printed surface. It is good because the upper whitening disappears.

Furthermore, in the present invention, it is possible to use, as a base, a sheet made of a composition in which the component (A) described above and the graft copolymer (B) and / or the graft copolymer (C) are blended. it can.

As described above, it is preferable to use a base in which the component (B) and / or the component (C) are blended with the component (A) because the effect that mechanical strength is increased and V cut suitability is good is exhibited.

When the sheet of the present invention is used in a place where a detergent is always used, such as a building material, particularly a kitchen, the stress crack resistance is improved by blending the following (E) polyester resin into the composition. preferable.

The (E) polyester resin has a crystallinity of infinitely close to 0 to 50%. Specifically, it has the following structural formula, 100 mol% of terephthalic acid, and ethylene glycol 42 to 32. Glycol-modified polycyclohexylene dimethylene terephthalate (PCTG) consisting of 1 mol% and 1,4-cyclohexanedimethanol 58-68 mol%; 1-50 mol% of isophthalic acid and 50-99 mol% of terephthalic acid as dicarboxylic acid components Acid-modified polycyclohexylene dimethylene terephthalate (PCTA), preferably consisting of 1 to 25 mol% of isophthalic acid and 75 to 99 mol% of terephthalic acid. Examples of PCTA include copolyester 1 consisting of 80 mol% terephthalic acid, 20 mol% isophthalic acid and 100 mol% 1,4-cyclohexanedimethanol, 95 mol% terephthalic acid, 5 mol% isophthalic acid Acid, copolyester 2 comprising 100 mol% of 1,4-cyclohexanedimethanol; and the like.

Further, polyethylene terephthalates represented by the following chemical formula are also preferable.

結晶 The heat of crystal melting of the component (E) by DSC (JIS K7121) is 15 (cal / g) or less, preferably 10 (cal / g) or less, and more preferably 7 (cal / g) or less. The viscosity of the component (E) is preferably 0.65 to 0.85 as an IV value. The component (E) can be used in combination of two or more as necessary.

The resin composition of the present invention containing the component (E) comprises (A) + 0.1 to 95% by weight of a completely amorphous polyester resin and (E) component of 5 to 99.9% by weight. (E) 50 to 99% by weight of a component;

(B) Graft copolymer obtained by graft-polymerizing (meth) acrylic acid ester and vinyl aromatic onto conjugated diene rubber particles, and graft-polymerizing (meth) acrylic ester and vinyl aromatic onto acrylic rubber particles At least one or more selected from the group consisting of (C) a graft copolymer and (D) a thermoplastic polyester elastomer obtained by the method,
Comprising.

In a preferred embodiment, the resin composition of the present invention containing the component (E) comprises (A) + 20 to 93% by weight of a completely amorphous polyester resin and (E) component 7 to 80% by weight. (E) 70 to 93% by weight of a component;
(B) Graft copolymer obtained by graft-polymerizing (meth) acrylic acid ester and vinyl aromatic onto conjugated diene rubber particles, and graft-polymerizing (meth) acrylic ester and vinyl aromatic onto acrylic rubber particles And at least one selected from the group consisting of (C) a graft copolymer and (D) a thermoplastic polyester-based elastomer, and 7 to 30% by weight,
Comprising. Although the resin composition of the present invention containing the component (E) has a smaller proportion of the component (A) than the resin composition described above, the main purpose is to obtain stress crack resistance. This is because it is assumed. Conversely, when properties of the sheet other than stress crack resistance are not so desired, the component (A) may be set to 0.1 to 95% by weight.

The components (A), (B), (C) and (D) are as described above.

The various compositions described above may contain appropriate amounts of additives.
Examples of such additives include flame retardants, release agents, weathering stabilizers, antioxidants, antistatic agents, heat stabilizers, lubricants, coloring agents, surfactants, reinforcing agents, fillers, and the like. Can be It is preferable to add a lubricant for the purpose of improving workability. Examples of the lubricant include hydrocarbons (low-molecular polyethylene, paraffin), fatty acids (stearic acid, hydroxystearic acid, complex stearic acid, oleic acid), aliphatic alcohols, and aliphatic amides (stearamide, oxystearamide). Oleylamide, erucylamide, ricinolamide, behenamide, methylolamide, methylenebisstearamide, methylenebisstearobenamide, higher fatty acid bisamic acid, stearamide, complex amide), aliphatic ester (n-butyl stearate) , Methylhydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, ester waxes), fatty acid metal soaps, and the like. Preferred are hydrocarbon-based and aliphatic ester-based, and more preferred are aliphatic esters.

樹脂 The resin composition of the present invention can be obtained by kneading the compound with, for example, a Banbury kneader, a single-shaft or twin-shaft kneader.

The resin composition of the present invention can be formed into a sheet having a desired size and thickness by using a calendering machine, a T-die extruder, or the like. The obtained sheet is hardly whitened at the time of embossing or heat bonding, and is particularly suitable for vacuum press molding, pressurized press molding, and membrane press molding, and can be used, for example, as various laminated decorative sheets.

The thickness of the resin sheet or the laminated resin sheet of the present invention is not particularly limited. For example, the transparent resin sheet has a thickness of 5 to 1000 μm, preferably $ 60 to 500 μm. The thickness is preferably from 500 to 500 µm, the thickness of the base is from 5 to 1000 µm, preferably from 60 to 500 µm, and the entire sheet is from 10 to 2000 µm, preferably from 120 to 1000 µm.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 17)
A method for measuring various characteristics will be described.
(1) Roll workability test The composition was kneaded with an 8-inch test roll device at a roll surface temperature of 190 ° C to test the workability.
〇: Kneading work was performed without any problem, and a sheet was obtained.
Δ: Although a sheet was obtained, stickiness occurred and the work was difficult.
×: Crystallization occurred, the sheet became cloudy, and a product could not be obtained.

(2) Mold Contamination Test The resin composition (pellet) was injection-molded on a resin plate having a length of 150 mm, a width of 25 mm, and a thickness of 4 mm under the following injection conditions, and a test was performed on the releasability from the mold.
FS-120 manufactured by Nissei Plastic Industry Co., Ltd.
Molding temperature: 250 ° C, 260 ° C, 280 ° C
Injection speed: 55 mm / sec Injection pressure: 800 kg / cm ²
Holding pressure: 600 kg / cm ²
Injection time: 8 seconds Cooling time: 45 seconds

(3) Plate-out test During the roll test, the metal surface condition of the roll was observed every 5 minutes.

(4) Izod impact test It was based on JIS K7110.
A test piece having a length of 6.35 mm, a width of 12.7 mm and a thickness of 6.4 mm was prepared by injection molding and evaluated. (With notch)

(5) Tensile strength and elongation Based on JIS K7113.
A No. 1 dumbbell test piece having a thickness of 1.0 mm was prepared by injection molding, and left at a temperature of 23 ° C. and a relative humidity of 50% (before the accelerated test) and a temperature of 60 ° C. and a relative humidity of 95% for 7 days (after the accelerated test) ) And evaluated.

(6) V-cut property test A predetermined amount of the resin compound was calendered to produce a 0.2 mm thick film. This sheet was left in an environment at a temperature of 60 ° C. and a relative humidity of 95% for 7 days, and then laminated on an MDF (medium density fiber board) by the following method. That is, a two-component curable adhesive mainly composed of an ethylene-vinyl acetate copolymer is rolled on MDF having a water content of 5 to 15%: length 240 mm × width 1200 mm × thickness 18 mm (Starwood: manufactured by Hokushin Plywood). After being applied in an amount of about 140 g / mm ^{2 by} a coating method, the film was laminated, and then pressed and cured at a pressure of 1 to 5 kg / cm ² for about 12 hours.

This MDF with a film was cut into a length of 600 mm × a width of 400 mm, and the MDF side was cut into a V-shape at an intermediate point of the length in the width direction at an opening angle of 90 degrees as shown in FIG. This was bent under the conditions of a processing temperature of 23 ± 2 ° C. and a bending speed of 1 mm / min to form a rectangular shape as shown in FIG.
The appearance of the bent portion was observed. ○ indicates “no abnormality” and × indicates “crack occurred”.
In the following examples, any of the following various resins was used.

(1) (A) Completely amorphous polyester resin Manufacturer: Eastman Chemical Company Product name: KODAR PETG 6763 (PET-G)
Composition: Copolymer type Glycol component: 70 mol% of ethylene glycol and 30 mol% of 1,4-cyclohexanedimethanol
Dicarboxylic acid component: Terephthalic acid Crystal component: 0%
Heat of crystal melting: Cannot be measured because it is completely amorphous

(2) Amorphous polyester resin Manufacturer: Unitika Trade name: MA-2101 (A-PET)
Composition: homo-type glycol component: ethylene glycol dicarboxylic acid component: terephthalic acid crystal component: partially

(3) (B) Graft copolymer (i)
Manufacturer: Kanebuchi Chemical Industry Product Name: Kaneace B-28
Composition: methacrylate / styrene / styrene / butadiene rubber graft copolymer Rubber particle diameter: 0.1 to 0.5 μm
(Ii)
Manufacturer: Kanebuchi Chemical Industry Product Name: Kaneace B-56
Composition: methacrylate / styrene / butadiene rubber graft copolymer Rubber particle diameter: 0.1 to 0.5 μm

(4) (C) Graft copolymer Manufacturer: Kanegafuchi Chemical Industry Product Name: Kaneace FM
Composition: methacrylic acid ester / acrylonitrile / butyl acrylate (acrylic rubber) graft copolymer Rubber particle diameter: 0.05 to 0.1 μm

(5) Other polymers (i)
Manufacturer: Asahi Kasei Kogyo Product name: Asaflex 810
Composition: styrene / butadiene block copolymer, styrene content 78%
Number average molecular weight 130,000 (ii)
Manufacturing company: Asahi Kasei Kogyo Product name: Tuffrene 125
Composition: Styrene / butadiene block copolymer Styrene content 40%
Number average molecular weight 80,000

(4) Additive (i)
Manufacturer: Ishihara Sangyo Product Name: CR90
Composition: rutile-type titanium oxide (ii)
Manufacturer: Mitsui Chemicals Product name: W-4051
Composition: Oxidized polyethylene wax The test results obtained are shown in Tables 1 and 2.

As can be seen from the above table, the resin composition of the present invention is excellent in various results, but those using a mere amorphous polyester resin instead of a completely amorphous polyester resin (Examples 10 and 11) Roll workability is remarkably inferior. The blends of (B) a graft copolymer and a polymer other than (C) (Examples 12 to 17) are excellent in physical properties, but are inferior in roll workability, mold contamination and plate-out properties. In the case where only a completely amorphous polyester resin is blended as a polymer component (Example 9), sufficient physical properties cannot be obtained.

Further, the kneading load torque of the resin compositions in Examples 3, 4, 8, and 9 in a mill was measured. The measurement conditions are shown below.
Mixer used: Toyo Seiki Seisakusho Labo Plastomill R-30 type Sample amount: 33 g
Test temperature: 160 ° C
Test rotation speed: 50.0 rpm
Preheating time: 120 seconds

The results obtained are shown in FIG. In FIG. 1, number 1 is Example 9, 2 is Example 8, 3 is Example 4, and 4 is Example 3. According to FIG. 1, the resin composition of the present invention has a high torque value in a short time and gelation is rapidly achieved, whereas the resin composition of Example 9 gelates until nearly 20 minutes. Was delayed, and the difference in workability between the two became apparent. That is, the resin composition of the present invention is quickly melted by kneading, and the dispersion of each component becomes uniform in a short time. However, the resin composition of Example 9 has a low melting point due to poor heat conductivity. It takes a long time to disperse each component.

(Examples 18 to 28)
A method for measuring various characteristics in the present example will be described.
(1) Roll workability test In accordance with Example 1.
(2) Mold Contamination Test According to Example 1.
(3) Izod impact test According to Example 1.
(4) Tensile strength and elongation According to Example 1.
(5) Haze (haze value) test Based on JIS K7105.
The thickness of the test piece was evaluated at 1 mm.
(6) V-cut suitability test The same as in Example 1.
(7) Bending whitening test In the above (6) V-cutting test, whitening of the appearance of the bent portion was observed. ○ represents “no whitening”, and Δ represents “whitening of dark colors, light white such as light gray without whitening”.
In this example, one of the following various resins was used.

(1) (A) Completely amorphous polyester resin manufacturing company: Eastman Chemical Company, trade name: KODAR PETG 6763 (PET-G)
Composition: copolymer type glycol component: 70 mol% of ethylene glycol and 30 mol% of 1,4-cyclohexanedimethanol
Dicarboxylic acid component: terephthalic acid crystal component: 0%
Heat of crystal melting: Cannot be measured because it is completely amorphous

(2) (D) Thermoplastic polyester elastomer manufacturer: manufactured by Du Pont-Toray Co., Ltd .: Hytrel 4057, 2551
Composition: Copolymer of hard segment (PBT) and soft segment (polyether)

(3) (B) Graft copolymer manufacturing company: Kanegafuchi Chemical Industry: Kaneace B-56
Composition: methacrylic acid ester / styrene / butadiene rubber graft copolymer rubber particle diameter: 0.1 to 0.5 μm

(4) (C) Graft copolymer manufacturing company: Kanegafuchi Chemical Co., Ltd. Product name: Kaneace FM
Composition: methacrylic acid ester / acrylonitrile / butyl acrylate (acrylic rubber) graft copolymer rubber Particle diameter: 0.05 to 0.1 μm

(5) Additive manufacturer Henkel Japan Roxyol G-78
Composition Mixture of metal soap and high molecular weight ester

(6) (F) Thermoplastic resin sheet (i) PVC sheet manufacturer Riken Vinyl Industry W500
Composition Polyvinyl chloride resin
(ii) PP sheet manufacturing company Riken Vinyl Industrial product name @W
Composition Polypropylene resin
(iii) PE sheet manufacturer Riken Vinyl Industry's trade name TPN
Composition Polyethylene resin

組成 Compositions were prepared in the formulations shown in Tables 3 to 5 and subjected to the various tests described above. The results are also shown in Tables 3 to 5.

(Example 29)
As a base layer, a resin sheet having a thickness of 80 μm was manufactured using a calendar manufacturing machine (the composition was the same as in Example 21), colored with titanium oxide and an organic pigment, and a printing layer of 1.5 ± 0.5 μm (Nippon Decor Co., Ltd.) Co., Ltd.). After the printing layer was cured, a solvent type two-component adhesive (AD527 / CATHY-92, Toyo Morton Co., Ltd.) was applied to the upper surface of the printing layer by a gravure coating method. After the application, the solvent was evaporated and scattered in a drying oven to form an adhesive layer (thickness: 2.5 ± 0.5 μ). The drying oven was provided with a drying zone of a floating system set at 75 ° C. to 85 ° C., and the resin sheet was passed through the drying zone for 18 seconds to 22 seconds. After the adhesive layer was dried, the resin sheet of Example 21 having a thickness of 80 μm, which was the upper layer, was overlaid and thermally fused with a metal roll.
Thereafter, the sheet was wound and left at room temperature of 40 ± 2 ° C. for 72 hours to cure the adhesive, thereby obtaining a product. The obtained laminated decorative sheet was examined for bending whitening property and V-cut suitability. Table 6 shows the results.

(Examples 30 to 34)
In Examples 30 to 34, the same test as in Example 16 above was performed by changing the underlayer as described below.
Example 31 is a test of a colored decorative sheet without providing a printing layer.

(Example 30)
Upper layer 80 μm thick, blended in Example 21, primary color Printed layer Printed woodgrain on underlying layer Underlayer 80 μm thick, colored in blended example 26 (toned with titanium oxide, organic pigment, etc.)

(Example 31)
Upper layer 80 μm thick, blended and colored in Example 21 Underlayer 80 μm thick, blended and colored in Example 26 (toned with titanium oxide, organic pigment, etc.)

(Example 32)
Upper layer 80 μm thick, blended in Example 21, primary color Printed layer Printed woodgrain on underlayer Underlayer 80 μm thick, manufactured by Riken Vinyl Industry Co., Ltd. (PVC sheet, W500 colored product)

(Example 33)
Upper layer 80 μm thick, blended in Example 21, primary color Printed layer Woodgrain print on underlayer Underlayer 80 μm thick, manufactured by Riken Vinyl Industry Co., Ltd. (PP sheet, OW colored product)

(Example 34)
Upper layer 80 μm thick, blended in Example 21, primary color Printed layer Printed woodgrain on underlayer Underlayer 80 μm thick, manufactured by Riken Vinyl Industry Co., Ltd. (PE sheet, TPN colored product)
Table 6 shows the results obtained in Examples 29 to 34.

(Examples 35-36)
Examples 35 and 36 are comparative examples in which the same material as in Examples 30 and 34 of the laminated sheet was used, the upper layer and the lower layer were reversed, and a decorative sheet in which the upper layer was a primary color and the lower layer was colored was laminated. The method of lamination and the test method are the same as those in Example 29.

(Example 35)
Upper layer 80 μm thick, blended in Example 26, primary color Printed layer Printed woodgrain on underlying layer Underlayer 80 μm thick, blended in Example 21, colored

(Example 36)
Uechi layer 80 μm thick, manufactured by Riken Vinyl Industry Co., Ltd. (PE sheet, TPN primary color)
Printing layer Wood-grained printing on the underlayer Underlayer thickness 80 μm, formulation of Example 21, coloring Results obtained in Examples 35 to 36 are shown in Table 7.

(Examples 37-75)
Using the materials shown below and in the formulations shown in Tables 8 to 11, (1) transfer foil / (2) 0.2 mm thick polyester sheet / (3) 0.15 mm thick polyester sheet were prepared, respectively. (2) The layers were laminated in the order of (3), and these were heat-sealed with a metal mirror roll at 150 ° C. to 160 ° C. for 40 seconds (nip pressure: 2.0 kg / cm, drum rotation speed: 2.0 (m / Min), drum circumference: 2.0 m). The polyester sheet was formed into a desired thickness by a T-die extruder.
Next, the laminated sheets were bonded to the following adherend using a membrane press machine (model name: KT-M-139, manufacturer name: Ben Horner). The bonding conditions were as follows: press temperature setting: top / bottom = 110 ° C./80° C., press time setting: preheating / pressurization = 60 seconds / 60 seconds, pressure: 4 kg / cm ² .
The adherend (MDF) is a plywood obtained by finely cutting wood chips such as softwood or rawan wood and pressing the wood chips. The adherend is cut into a shape of a door to be incorporated in a system kitchen or the like (size: about 150 mm × 200 mm, thickness: about 18 mm), and further subjected to curved surface processing (about 3R to 10R). The top surface is engraved with a decorative groove (called a router).
Before bonding, for example, a urethane-based adhesive (adhesive product name: 34333 manufactured by Hemimitin Co., Ltd. and a hardening agent product name: Hardner D manufactured by the company) are put on the surface of the door-shaped MDF in a weight ratio of 100: 5).

Material used in this example (1) Transfer foil Product name: UV-03 manufactured by Keihan Oike Transfer Co., Ltd.
Type: Acrylic transfer foil, 12 μm thick

(2) Polyester sheet (A) Completely amorphous polyester resin Manufacturer: Eastman Chemical Company Product name: KODAR PETG 6763 (PET-G)
Composition: Copolymer type Glycol component: 70 mol% of ethylene glycol and 30 mol% of 1,4-cyclohexanedimethanol
Dicarboxylic acid component: Terephthalic acid Crystal component: 0%
Heat of crystal melting: Cannot be measured because it is completely amorphous

(B) Graft copolymer Manufacturing company: Kanegafuchi Chemical Industry Product name: Kaneace B-56
Composition: methacrylate / styrene / butadiene rubber graft copolymer (MBS)
Rubber particle diameter: 0.1 to 0.5 μm

(D) Thermoplastic polyester-based elastomer Manufacturer: Dupont Toray Product name: Hytrel 2551 (Hytrel)
Composition: Copolymer of hard segment (PBT) and soft segment (polyether)

(E) Polyester resin (i)
Manufacturer: Eastman Chemical Company Product name: EASTER PCTG 5445 (PCTG)
Composition: copolymer type 100% by mole of terephthalic acid, 42 to 32% by mole of ethylene glycol and 58 to 68% by mole of 1,4-cyclohexanedimethanol glycol-modified polycyclohexylene dimethylene terephthalate Crystal component (crystallinity): trace amount of crystal Heat of fusion: 2.6 (cal / g)
(Ii)
Manufacturer: Eastman Chemical Company Product name: THERMX PCTA 6761 (PCTA)
Composition: copolymer type An acid consisting of 1-50 mol% of isophthalic acid and 50-99 mol% of terephthalic acid as the dicarboxylic acid component, preferably 1-25 mol% of isophthalic acid and 75-99 mol% of terephthalic acid Modified polycyclohexylene dimethylene terephthalate Crystal heat of fusion: 5.5 (cal / g)

(3) Polyester sheet Manufacturer: manufactured by Riken Vinyl Industry Co., Ltd. Product name: RIVESTAR SET351 FZ13359
Composition: copolymer type Crystalline component (crystallinity): 0%

The following test was performed about the obtained molded object.
-Transparency: Judged visually. The judgment levels were: ：: good transparency, Δ: slight cloudiness, ×: cloudy.
-Pencil hardness test: according to JIS K5400 (load: 200g)
-Stress crack test with detergent: Kitchen detergent (Made by Kao Corporation, MagicLin) is sufficiently applied to the formed sample, left at room temperature for 24 hours, and then subjected to an environment of 50 ° C for 90 minutes, and further 0 ° C for 90 minutes. After storage, the presence or absence of cracks on the surface of the molded product was visually judged. The judgment levels were as follows: ：: no cracks, Δ: slight cracks (about 1 to 10), ×: many cracks (10 or more), XX: cracks occurred on the entire surface. The results are shown in Tables 8 to 11.

According to the present invention, workability, moldability, excellent physical properties such as impact resistance, excellent transparency, almost no plate-out, hardly whitened at the time of embossing or hot bonding, especially membrane press molding, A resin composition and a resin sheet suitable for vacuum press molding, compressed air press molding, and the like are provided.

FIG. 8 is a view showing the results of measuring the kneading load torque of the resin compositions in Examples 3, 4, 8, and 9 in a mill. It is the figure which laminated | stacked the MDF which cut the resin sheet of this invention in V cut. It is the figure which laminated | stacked the resin sheet of this invention on the VDF-cut MDF, and bent this and made it a right angle.

Claims (8)

A composition containing (A) 50 to 99.9% by weight of a completely non-crystalline polyester resin and (D) 0.1 to 50% by weight of a thermoplastic polyester elastomer, further contains a hydrocarbon lubricant, a fatty acid lubricant, and a fat. A resin sheet obtained by adding one or more lubricants selected from aliphatic alcohol-based lubricants, aliphatic amide-based lubricants, aliphatic ester-based lubricants and aliphatic metal soap-based lubricants, and molding the resulting molding material. The resin sheet according to claim 1, wherein the resin sheet is colored and / or printed on the surface. 積 層 A laminated resin sheet obtained by laminating two or more layers of the sheet according to claim 1. A laminated resin sheet obtained by laminating two or more layers of the sheet according to claim 2. 積 層 A laminated resin sheet obtained by laminating the resin sheet according to claim 1 as an upper ground and the resin sheet according to claim 2 as a base. 積 層 A laminated resin sheet obtained by using the resin sheet according to claim 1 or 2 as an upper ground, using a thermoplastic resin sheet as a base, and laminating both. The resin sheet according to claim 1 is used as an upper layer, and as a base which is colored and / or printed on the surface, (A) 50 to 99% by weight of a completely amorphous polyester resin and conjugated diene rubber particles (B) Graft copolymer obtained by graft polymerization of (meth) acrylate and vinyl aromatic and / or graft polymer of (meth) acrylate and vinyl aromatic on acrylic rubber particles ( C) A laminated resin sheet obtained by using a sheet comprising 1 to 50% by weight of a graft copolymer and laminating both. 積 層 The laminated resin sheet according to claim 7, wherein the resin sheet according to claim 2 is used as the upper ground.

Images