JP4521011B2 - Laminated resin sheet - Google Patents

Description

  The present invention relates to a laminated resin sheet.

Conventionally, laminated decorative sheets have been widely used by being bonded to metal or wood-based materials such as furniture, cabinets, joinery, desks and cupboards.
The laminated decorative sheet is also used as a single sheet, or as a laminated decorative sheet in which a sheet is laminated on a top, a base, and a center 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 faithfully.

Examples of such a conventional laminated decorative sheet include a sheet described in Patent Document 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 is called “non-crystalline”, but has a part of crystallinity.

Patent Document 2 describes a hard shrink film. This comprises an amorphous polyester resin component, a polymer block component mainly composed of at least one vinyl aromatic hydrocarbon, and a polymer block mainly composed of at least one conjugated diene derivative. And a polymer component made of the vinyl aromatic hydrocarbon.
According to this prior art, it is said that a laminated decorative sheet and a hard shrinkable film having excellent moldability and impact resistance can be obtained.

  Furthermore, Patent Document 3 describes an impact modifier for polyalkylene terephthalate resins. 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, it is said that a resin composition excellent in impact resistance can be obtained.

Japanese Patent Laid-Open No. 7-24979 JP-A-62-124928 JP-A-2-129266

However, conventional resin compositions and laminated decorative sheets have problems in that whitening occurs during embossing, heat bonding, and bending during secondary processing, and transparency is poor. Further, there is a problem that plate-out occurs during roll molding (calender molding, emboss molding) or injection molding.
Conventionally, in addition to a resin sheet having transparency, a resin sheet having a base colored or printed sheet has been widely used. In this case, in order to provide a deeper design, the upper layer is generally 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 an upper layer has a problem that it is easy to whiten when bent and has poor workability.

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

Membrane press molding refers to heating a thermoplastic decorative sheet having a desired thickness or a desired color or surface printing to the vicinity of its softening point, which is then applied to an adherend of a predetermined shape, for example, the shape of a door of a kitchen set. Cover the adherend with a complicated curved surface like this, and then apply a stretchable membrane (film-like material), such as a rubber film, and apply air or liquid pressure to it, and adhere to its contour. A decorative sheet is pasted on.
Moreover, the basic principle of vacuum press molding and pressure press molding is the same 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. This is a molding method.

As a result of intensive studies, the present inventors have been able to solve the conventional problems as described above.
That is, according to the first aspect of the present invention, (A) the dicarboxylic acid component is terephthalic acid, and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. A composition containing 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, and further, a hydrocarbon lubricant, a fatty acid lubricant, and an aliphatic alcohol system lubricant, one or more lubricants selected from aliphatic amide-based slipping agent Contact and aliphatic metal soap lubricant was added, a resin sheet obtained by molding material obtained by film by calender making machine,
As a base on which coloring and / or printing has been performed on the surface, (A) the dicarboxylic acid component is terephthalic acid, and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. (B) Graft copolymer and / or acrylic obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles Obtained by forming a molding material comprising 1 to 50% by weight of (C) graft copolymer obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic on rubber-based rubber particles with a calendering machine Using the sheet
This is a laminated resin sheet obtained by laminating both the upper and lower layers.
Furthermore, 2nd of this invention is a laminated resin sheet of Claim 1 using said resin sheet in which the resin sheet as said upper layer is colored and / or printed on the surface.

  According to the present invention, it has excellent physical properties such as workability, moldability, impact resistance, excellent transparency, almost no plate-out, and is not easily whitened during embossing or heat bonding. A resin sheet suitable for vacuum press molding, pneumatic press molding and the like is provided.

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

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

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

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

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

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

  The resin composition of the present invention is obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles on (B) graft copolymer. Whether the blend is blended, or the fully amorphous polyester resin component (A) is blended with (C) a graft copolymer obtained by graft polymerization of (meth) acrylate to acrylic rubber particles Alternatively, it can be obtained by blending the above-mentioned (B) graft copolymer and (C) into 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 polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles.
Conjugated dienes used for the preparation of conjugated diene rubber particles are olefins having a conjugated double bond, such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1, and the like. Examples include 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.

  Preparation of the conjugated diene rubber particles is carried out by polymerizing the conjugated diene as described above, but it may be further copolymerized using a vinyl aromatic or other copolymerizable monomer. Examples of the vinyl aromatic for this purpose include styrene, α-methylstyrene, α-ethylstyrene, or a nucleus-substituted derivative thereof such as vinyltoluene, isopropenyltoluene, chlorostyrene, and aromatic vinylidene. Other copolymerizable monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinylidene cyanide; and the like.

  Furthermore, you may make it bridge | crosslink using a crosslinking agent. As the crosslinkable monomer, monomers having two or more reactive double bonds, for example, aromatic divinyl monomers such as divinylbenzene; ethylene glycol di (meth) acrylate, butylene glycol di Alkane polyol polyacrylates such as (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate; In particular, butylene glycol diacrylate and hexanediol diacrylate are preferably used.

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

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

  The resulting conjugated diene rubber particles preferably have a particle size of 0.05 to 1.0 μm. More preferably, it is 0.05-0.5 micrometer.

  Next, (B) graft copolymer is prepared by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles. As (meth) acrylic acid ester, those having 1 to 8 carbon atoms are suitable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl ( And (meth) acrylate and 2-ethylhexyl (meth) acrylate. These can also be used in combination. Of these, methyl (meth) acrylate is desirable. As the vinyl aromatic, those exemplified above can be used.

  In the graft polymerization of (meth) acrylic acid ester and vinyl aromatic, other components, that is, other copolymerizable monomers, cross-linking agents, etc. can be used as needed. . As other copolymerizable monomers and crosslinking agents, 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 (meth) acrylic acid ester, vinyl aromatic and other components.

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

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

  Acrylic rubber particles are prepared by polymerizing the acrylic ester as described above, but may be further copolymerized using a vinyl aromatic or other copolymerizable monomer. Moreover, you may make it bridge | crosslink using a crosslinking agent. Examples of these vinyl aromatics, other copolymerizable monomers, and crosslinking agents include those described in the section of the above (B) graft copolymer.

  The acrylic rubber particles preferably comprise 1 to 65% by weight of acrylic ester, 0 to 35% by weight of vinyl aromatic and 0 to 35% by weight of other copolymerizable monomers. A small amount of the crosslinking agent is used, and a specific amount is appropriately selected.

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

  The obtained acrylic rubber particles preferably have a particle diameter of 0.05 to 1.0 μm. More preferably, it is 0.05-0.5 micrometer.

  Next, a graft copolymer (C) is prepared by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to acrylic rubber particles. As (meth) acrylic acid ester, those having 1 to 8 carbon atoms are suitable, and those described in the column of (B) Graft copolymer are exemplified. Examples of the vinyl aromatic include those described in the column of the (B) graft copolymer.

  In the graft polymerization of the (meth) acrylic acid ester, other components, that is, other copolymerizable monomers, cross-linking agents, and the like can be used as necessary. As other copolymerizable monomers and crosslinking agents, 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 (meth) acrylic acid ester and other components.

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

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

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

  The blending ratio of the resin composition of the present invention is as follows: (A) 50 to 99% by weight of completely amorphous polyester resin and (B) 1 to 50% by weight of graft copolymer, preferably (A) completely amorphous polyester It is preferable to use 55 to 92% by weight of the resin and 8 to 45% by weight of the (B) graft copolymer.

  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) The crystalline polyester resin is preferably 55 to 92% by weight and (C) the graft copolymer 8 to 45% by weight.

  When (B) the graft copolymer and (C) are used in combination, (A) 50 to 98% by weight of completely amorphous polyester resin, (B) 1 to 49% by weight of graft copolymer and (C) The graft copolymer is preferably 1 to 49% by weight. However, the sum 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) a completely amorphous polyester resin 50 to 99.9 wt% and (D) a thermoplastic polyester elastomer 0.1 to 50 wt%. Is to provide.
As the (D) thermoplastic polyester elastomer, for example, the following general formula (1) or (2)

A terephthalic acid crystalline polyester hard segment represented by the formula (polybutylene terephthalate (PBT) or polybutylene naphthalate (PBN)), and a general formula (3)

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

  (D) By setting the molecular weight of the thermoplastic polyester elastomer in the above range, the resulting resin sheet has better physical properties such as impact resistance, tensile strength, cold resistance, and moldability.

  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, such as impact resistance, can be imparted.

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

  The hard component is an aromatic polyester, the soft component is an aliphatic polyester, the hard component is an aromatic polyester, the soft component is an aliphatic polyester (for example, an aliphatic lactone elastomer), and the hard component is a polybutylene. A (co) polymer having a phthalate and a soft component composed of an aliphatic polyether can be mentioned.

  The blending amounts of the component (A) and the component (D) are 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.

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

  The composition in which the component (A) and the component (D) are blended can be molded into a sheet by means described below, and this is used as a resin sheet (hereinafter referred to as a transparent resin sheet) as a single layer. Can be used. The transparent resin sheet thus obtained is excellent in mechanical strength and transparency, hardly whitened during bending, and excellent in design. This transparent resin sheet can be colored by known means and / or the surface may be printed.

  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 layers of colored and / or surface-printed resin sheets Examples thereof include those using the above-described resin sheet colored and / or printed on the surface as a sheet and a base, and a transparent resin sheet as a top. In this case, it goes without saying that various intermediates can be applied as necessary, and this aspect is also included in the scope of the present invention.

  Apart from this, in the laminated resin sheet of the present invention, a sheet made of the following thermoplastic resin (F) can be used as a base.

  As the thermoplastic resin (F) used in the present invention, polyvinyl chloride, polyolefin (polyethylene, polypropylene, propylene-ethylene copolymer), (meth) acrylate, polycarbonate, polystyrene, AS-based resin, ABS-based resin, polyester-based resin, polyurethane-based, polyamide-based and the like are generally listed. This component (F) can also be processed into a sheet by means described below. When the component (F) is used as a base, the top is preferably the above transparent resin sheet or a colored and / or printed resin sheet. It is good because you can no longer see the whitening.

  Furthermore, in the present invention, a sheet made of a composition comprising the component (A) described above and (B) the graft copolymer and / or (C) the graft copolymer may be used as the base. it can.

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

  In addition, when the sheet | seat of this invention is used for the place which always uses detergent, such as building materials, especially a kitchen, stress crack resistance improves by mix | blending the (E) polyester-type resin shown below into a composition. preferable.

  This (E) polyester-based resin has a crystallinity as close as possible to 0 to 50%, and specifically has the following structural formula: 100 mol% terephthalic acid, ethylene glycol 42 to 32 Glycol modified polycyclohexylene dimethylene terephthalate (PCTG) consisting of 58% to 68% by mole of 1,4-cyclohexanedimethanol; 1 to 50% by mole of isophthalic acid and 50 to 99% by mole of terephthalic acid as dicarboxylic acid component Preferably, acid-modified polycyclohexylene dimethylene terephthalate (PCTA) consisting of 1 to 25 mol% isophthalic acid and 75 to 99 mol% 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% 1,4-cyclohexanedimethanol; and the like.

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

  The heat of crystal melting of component (E) by DSC method (JIS K7121) is 15 (cal / g) or less, preferably 10 (cal / g) or less, more preferably 7 (cal / g) or less. The viscosity of the component (E) is preferably 0.65 to 0.85 as the IV value. Moreover, (E) component can also be used in combination of 2 or more types as needed.

  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) 5 to 99.9% by weight of the component (A) + (E) component 50 to 99% by weight;

(B) Graft copolymer obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles, and (meth) acrylic acid ester and vinyl aromatic to graft polymerization of acrylic rubber particles. 1 to 50% by weight of at least one or more selected from the group consisting of (C) graft copolymer and (D) thermoplastic polyester elastomer obtained by
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-based resin and (E) 7 to 80% by weight of the component (A) + (E) 70-93 weight% of components,
(B) Graft copolymer obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles, and (meth) acrylic acid ester and vinyl aromatic to graft polymerization of acrylic rubber particles. 7 to 30% by weight of at least one selected from the group consisting of (C) a graft copolymer and (D) a thermoplastic polyester-based elastomer obtained by
Comprising. In addition, although the resin composition of this invention which mix | blended (E) component has a small compounding ratio of (A) component compared with the resin composition demonstrated previously, this is the main objective to obtain stress crack resistance. This is because it is assumed. Conversely, if the sheet properties 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, mold release agents, weather resistance stabilizers, antioxidants, antistatic agents, thermal stabilizers, lubricants, colorants, surfactants, reinforcing agents, fillers, and the like. It is done. In addition, it is preferable to mix | blend a lubricant for the purpose of improving workability. Lubricants include hydrocarbons (low molecular polyethylene, paraffin), fatty acids (stearic acid, hydroxystearic acid, complex stearic acid, oleic acid), aliphatic alcohols, aliphatic amides (stearamide, oxystearamide) used oleylamide, Erushiruamido, ricinoleamide, behenamide, methylol amides, methylene bis stearamide, methylene bis stearoamide behenic amide, bisamides acid of higher fatty acids, stearamide, a composite amide), fatty acid metal soap group such it is Ru can.

  The resin composition of the present invention can be obtained by kneading the compound with, for example, a Banbury kneader, a uniaxial or biaxial kneader.

  Moreover, the resin composition of this invention can be shape | molded into a sheet | seat of desired size and thickness using a calendar manufacturing machine, a T-die extruder, etc. The obtained sheet is not easily whitened at the time of embossing or heat bonding, and is particularly suitable for vacuum press molding, pressure 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. In the case of a laminated resin sheet, the top is 5 to 1000 μm, preferably 60 The base is 5 to 1000 μm, preferably 60 to 500 μm, and the entire sheet is 10 to 2000 μm, preferably 120 to 1000 μm.

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

(Examples 1-17)
A method for measuring various characteristics will be described.
(1) Roll workability test The blend was kneaded with an 8-inch test roll apparatus having a roll surface temperature of 190 ° C to test workability.
A: A kneading operation was completed without any problem, and a sheet was obtained.
Δ: Although a sheet was obtained, stickiness occurred and the operation was difficult.
X: Crystallization occurred, the sheet became clouded and a product could not be obtained.

(2) Mold Contamination Test A resin plate having a length of 150 mm, a width of 25 mm, and a thickness of 4 mm was injection-molded under the following injection conditions to test the peelability 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 state of the roll was observed every 5 minutes.

(4) Izod impact test Conforms to JIS K7110.
Test pieces having a length of 6.35 mm, a width of 12.7 mm, and a thickness of 6.4 mm were prepared and evaluated by injection molding. (With notch)

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

(6) V-cut property test A predetermined amount of resin blend was calendered to produce a 0.2 mm thick film. This sheet was allowed to stand in an environment of 60 ° C. and 95% relative humidity for 7 days, and then laminated on MDF (medium density fiber board) by the following method. That is, MDF with a moisture content of 5 to 15%: length 240 mm × width 1200 mm × thickness 18 mm (Starwood: manufactured by Hokushin Plywood) roll with a two-component curable adhesive mainly composed of ethylene-vinyl acetate copolymer After coating 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.

The MDF with a film was cut into a length of 600 mm and a width of 400 mm, and the MDF side was cut into a V shape at an opening angle of 90 degrees as shown in FIG. 2 in the width direction at the midpoint of the length. 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 right angle as shown in FIG.
The appearance of the bent part was observed. ○ was “no abnormality” and × was “crack occurred”.
In the following example, one of the following various resins was used.

(1) (A) Completely amorphous polyester-based resin Manufacturing company: Eastman Chemical Co., Ltd. Product name: KODAR PETG 6763 (PET-G)
Composition: Copolymer type Glycol component: 70 mol% ethylene glycol and 30 mol% 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 Product name: MA-2101 (A-PET)
Composition: Homotype Glycol component: Ethylene glycol Dicarboxylic acid component: Terephthalic acid Crystal component: Partially contained

(3) (B) Graft copolymer (i)
Manufacturing company: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-28
Composition: Methacrylate / styrene / styrene / butadiene rubber graft copolymer Rubber particle size: 0.1 to 0.5 μm
(Ii)
Manufacturing company: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-56
Composition: Methacrylic acid ester / styrene / butadiene rubber graft copolymer Rubber particle size: 0.1 to 0.5 μm

(4) (C) Graft copolymer Manufacturer: Kaneka Chemical Co., Ltd. Trade name: Kane Ace FM
Composition: Methacrylate / acrylonitrile / butyl acrylate (acrylic rubber) graft copolymer Rubber particle size: 0.05 to 0.1 μm

(5) Other polymers (i)
Manufacturer: Asahi Kasei Kogyo Brand name: Asaflex 810
Composition: Styrene / butadiene block copolymer Styrene content 78%
Number average molecular weight 130,000 (ii)
Manufacturer: Asahi Kasei Kogyo Brand name: Toughprene 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 titanium oxide (ii)
Manufacturing company: 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 simple amorphous polyester resin instead of a completely amorphous polyester resin (Examples 10 and 11), The roll workability is extremely inferior. In addition, (B) graft copolymers and those blended with polymers other than (C) (Examples 12 to 17) are excellent in physical properties, but inferior in roll workability, mold contamination, and plate-out properties. When a completely amorphous polyester resin alone is blended as a polymer component (Example 9), sufficient physical properties cannot be obtained.

In addition, the kneading load torque in the mill of the resin composition in Examples 3, 4, 8 and 9 was measured. The measurement conditions are shown below.
Used mixer: Labo Plast Mill R-30 type manufactured by Toyo Seiki Seisakusho Sample amount: 33g
Test temperature: 160 ° C
Test rotation speed: 50.0 rpm
Preheating time: 120 seconds

  The obtained results 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 torque value of the resin composition of the present invention increases in a short time and gelation is achieved quickly, whereas the resin composition of Example 9 gels until it is close to 20 minutes. However, the difference in workability between the two became clear. That is, the resin composition of the present invention rapidly melts by kneading and the dispersion of each component becomes uniform in a short time, but the resin composition of Example 9 has a slow melting due to poor thermal conductivity, It takes a long time to disperse each component.

(Examples 18 to 28)
A method for measuring various characteristics in this example will be described.
(1) Roll workability test According to Example 1.
(2) Mold contamination test According to Example 1.
(3) Izod impact test According to Example 1.
(4) Tensile strength, elongation According to Example 1.
(5) Haze (cloudiness value) test Conforms to JIS K7105.
The thickness of the test piece was evaluated at 1 mm.
(6) V-cut suitability test According to Example 1.
(7) Bending whitening test The whitening of the appearance of the bent portion was observed in the above (6) V-cut test. ○ is “no whitening”, and Δ is “dark whitening, light white such as light gray does not whiten”.
In this example, any of the following various resins was used.

(1) (A) Completely amorphous polyester resin manufacturer: Eastman Chemical Co., Ltd. Trade name: KODAR PETG 6763 (PET-G)
Composition: Copolymer type glycol component: Ethylene glycol 70 mol% and 1,4-cyclohexanedimethanol 30 mol%
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: Toray DuPont brand name: Hytrel 4057, 2551
Composition: Chemical structure is a copolymer of hard segment (PBT) and soft segment (polyether)

(3) (B) Graft copolymer manufacturer: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-56
Composition: Methacrylic acid ester / styrene / butadiene rubber graft copolymer rubber Particle size: 0.1 to 0.5 μm

(4) (C) Graft copolymer manufacturer: Kaneka Chemical Co., Ltd. Trade name: Kane Ace FM
Composition: Methacrylate / acrylonitrile / butyl acrylate (acrylic rubber) graft copolymer rubber Particle size: 0.05 to 0.1 μm

(5) Additive manufacturing company Henkel Japan product name 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 product name W500
Composition Polyvinyl chloride resin
(ii) PP sheet manufacturer Riken Vinyl Industry product name 〇W
Composition Polypropylene resin
(iii) PE sheet manufacturer Riken Vinyl Industry product name TPN
Composition Polyethylene resin

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

(Example 29)
As the underlayer, a resin sheet having a thickness of 80 μm is manufactured with a calendar manufacturing machine (formulation is 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) Wood grain). After the printing layer was cured, a solvent type two-component adhesive (Toyo Morton Co., Ltd. AD527 / CATHY-92) was applied to the upper surface of the printing layer by a gravure coating method. After coating, the solvent was evaporated and scattered in a drying furnace to provide an adhesive layer (thickness 2.5 ± 0.5 μm). The drying furnace was provided with a floating drying zone set at 75 ° C. to 85 ° C., and the resin sheet was allowed to pass through for 18 to 22 seconds. After the adhesive layer was dried, the resin sheet of Example 21 having a thickness of 80 μm as the upper layer was stacked and heat-sealed with a metal roll.
Thereafter, the sheet was wound up and allowed to stand at room temperature 40 ± 2 ° C. for 72 hours in order to cure the adhesive, and a product was obtained. The resulting laminated decorative sheet was examined for folding whitening and V-cut suitability. The results are shown in Table 6.

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

(Example 30)
Upper layer thickness 80μm, composition of example 21, primary color Printing layer Wood-grain printing on underlayer Underlayer thickness 80μm, coloring in composition of example 26 (toning with titanium oxide, organic pigment, etc.)

(Example 31)
Upper layer thickness 80 μm, composition of Example 21, coloring Coloring foundation layer thickness 80 μm, composition of Example 26, coloring (toned with titanium oxide, organic pigment, etc.)

(Example 32)
Upper layer thickness 80 μm, composition of Example 21, primary color Printing layer Wood-grain printing on underlayer Underlayer thickness 80 μm, manufactured by Riken Vinyl Industry Co., Ltd. (PVC sheet, W500 colored product)

(Example 33)
Upper layer thickness 80 μm, composition of Example 21, primary color Printing layer Wood-grain printing on underlayer Underlayer thickness 80 μm, manufactured by Riken Vinyl Industry Co., Ltd. (PP sheet, OW colored product)

(Example 34)
Upper layer thickness 80 μm, composition of Example 21, primary color Printing layer Wood-grain printing on underlayer Underlayer thickness 80 μm, manufactured by Riken Vinyl Industry Co., Ltd. (PE sheet, TPN colored product)
The results obtained in Examples 29-34 are shown in Table 6.

(Examples 35-36)
Example 35 and Example 36 are comparative examples in which the same materials as those in Example 30 and Example 34 of the laminated sheet are used, the top and the base are reversed, and a decorative sheet having the top and the base is colored. The laminating method and the test method are the same as in Example 29.

(Example 35)
Upper layer thickness 80 μm, formulation of Example 26, primary color Printing layer Woodgrain printing on underlayer Underlayer thickness 80 μm, formulation of Example 21 and coloring

(Example 36)
Upper layer thickness 80μm, manufactured by Riken Vinyl Industry Co., Ltd. (PE sheet, TPN primary color)
Printing layer Wood-grain printing on the underlayer Underlayer thickness 80 μm, formulation of Example 21, coloring Table 7 shows the results obtained in Examples 35-36.

(Examples 37 to 75)
(1) Transfer foil / (2) 0.2 mm thick polyester sheet / (3) 0.15 mm thick polyester sheet were prepared using the materials shown below and in the formulations shown in Tables 8 to 11, respectively (1) (2) The layers were laminated in the order of (3), and these were heat-sealed for 40 seconds with a metal mirror roll at 150 ° C. to 160 ° C. (nip pressure: 2.0 kg / cm drum rotation speed: 2.0 (m / Min), drum circumference: 2.0 m). The polyester sheet is a film formed to a desired thickness with a T-die extruder.
Next, the laminated sheet was bonded to the following adherend using a membrane press (model name: KT-M-139, manufacturer name: Ben Honer). 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 a wood chip such as a conifer or lauan wood and pressing it to harden it. The adherend is cut into a door shape incorporated in a system kitchen or the like (size: about 150 mm × 200 mm, thickness: about 18 mm) and curved surface processing (about 3R to 10R). A decorative groove is engraved on the top (called a router).
Before bonding, for example, a urethane-based adhesive (adhesive product name: 34333 manufactured by Henmy Tin Co., Ltd. and a hardener product name: Hardener D manufactured by the company was used as 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, 12μm thickness

(2) Polyester sheet (A) Completely amorphous polyester resin Manufacturer: Eastman Chemical Co., Ltd. Product name: KODAR PETG 6763 (PET-G)
Composition: Copolymer type Glycol component: 70 mol% ethylene glycol and 30 mol% 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 Manufacturer: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-56
Composition: Methacrylate / Styrene / Butadiene Rubber Graft Copolymer (MBS)
Rubber particle diameter: 0.1 to 0.5 μm

(D) Thermoplastic polyester-based elastomer Manufacturing company: Toray DuPont product name: Hytrel 2551 (Hytrel)
Composition: Chemical structure is a copolymer of hard segment (PBT) and soft segment (polyether)

(E) Polyester resin (i)
Manufacturer: Eastman Chemical Company Name: EASTER PCTG 5445 (PCTG)
Composition: Copolymer type Glycol-modified polycyclohexylenedimethylene terephthalate composed of 100 mol% terephthalic acid, 42-32 mol% ethylene glycol and 58-68 mol% 1,4-cyclohexanedimethanol Crystal component (crystallinity): Trace amount Crystal Heat of fusion: 2.6 (cal / g)
(Ii)
Manufacturer: Eastman Chemical Co., Ltd. Product Name: THERMX PCTA 6761 (PCTA)
Composition: Copolymer type Acid comprising 1-50 mol% isophthalic acid and 50-99 mol% terephthalic acid as dicarboxylic acid component, preferably 1-25 mol% isophthalic acid and 75-99 mol% terephthalic acid Modified polycyclohexylene dimethylene terephthalate Heat of crystal fusion: 5.5 (cal / g)

(3) Polyester sheet Manufacturer: Riken Vinyl Kogyo Co., Ltd. Trade name: RIVESTAR SET351 FZ13359
Composition: Copolymer type Crystal component (crystallinity): 0%

The following test was done about the obtained molded object.
-Transparency: Judged visually. The judgment levels are ○: good transparency, Δ: slight white turbidity, ×: white turbidity.
・ Pencil hardness test: according to JIS K5400 (load: 200 g)
・ Stress crack test with detergent: A kitchen detergent (trade name “Magicline” manufactured by Kao Co., Ltd.) is sufficiently applied to the molded sample, left at room temperature for 24 hours, and then placed in an environment of 50 ° C. × 90 minutes and further 0 ° C. × 90 minutes. After storage, the presence or absence of cracks on the surface of the molded product was visually determined. Judgment levels are: ◯: no crack, Δ: slight crack (about 1 to 10), x: many cracks (10 or more), xx: cracks are generated on the entire surface. The results are shown in Tables 8-11.

  According to the present invention, it has excellent physical properties such as workability, moldability, impact resistance, excellent transparency, almost no plate-out, and is not easily whitened during embossing or heat bonding. A resin composition and a resin sheet suitable for vacuum press molding, compressed air press molding, and the like are provided.

It is a figure which shows the measurement result of the kneading | mixing load torque in the mill of the resin composition in Example 3, 4, 8 and 9. It is the figure which laminated the resin sheet of this invention on V cut MDF. It is the figure which laminated the resin sheet of this invention on V cut MDF, bent this, and made it right angle.

Claims (2)

As an upper layer, (A) a completely amorphous polyester resin 50 in which the dicarboxylic acid component is terephthalic acid and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. to 99.9% by weight and (D) a composition containing from 0.1 to 50 wt% thermoplastic polyester elastomer, further hydrocarbon lubricant, a fatty acid-based lubricant, aliphatic alcohol lubricants, aliphatic amide-based slipping agent one or more lubricants selected from Contact and aliphatic metal soap lubricant was added, a resin sheet obtained by molding material obtained by film formation using a calender maker,
As a base on which coloring and / or printing has been performed on the surface, (A) the dicarboxylic acid component is terephthalic acid, and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. (B) Graft copolymer and / or acrylic obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic to conjugated diene rubber particles Obtained by forming a molding material comprising 1 to 50% by weight of a (C) graft copolymer obtained by graft polymerization of (meth) acrylic acid ester and vinyl aromatic onto rubber-based rubber particles using a calendar making machine Use resin sheet,
A laminated resin sheet obtained by laminating both the upper and lower layers.   The laminated resin sheet according to claim 1, wherein the resin sheet as the top is colored and / or printed on the surface.

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