JP7259473B2 - Resin composition, molded article and laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having good adhesion to aluminum, polycarbonate resin and polyvinyl chloride resin, a molded article of the resin composition, a laminate having a layer containing the resin composition, and a construction material. .

Soft polyvinyl chloride resin substrates are frequently used as substrates for construction materials such as wallpapers and decorative sheets because they are flexible and have good moldability. In addition, building materials made of soft polyvinyl chloride resin are also used with embossing or foaming for applications that require improved texture and design. Soft polyvinyl chloride resin is also used for automobile interior parts because it has excellent flexibility and feel and is low in cost. As the demand for weight reduction increases, there is a need to reduce the weight of soft polyvinyl chloride resin parts by laminating them with polyolefin resin or polycarbonate resin having a lower specific gravity. Furthermore, when used as a member having strength as well as weight reduction, it has a laminated structure with a metal plate such as aluminum.

Various attempts have been made to improve the adhesive strength between layers of a laminate containing a soft polyvinyl chloride resin layer, a polyolefin resin layer and/or a saponified ethylene/vinyl acetate copolymer layer.
For example, Patent Document 1 discloses that an ethylene/vinyl acetate copolymer having a high vinyl acetate content and an ethylene/vinyl acetate copolymer having a low vinyl acetate content are placed between a soft polyvinyl chloride resin layer and a polyolefin resin layer. It is disclosed that the adhesive strength at the interface of the soft polyvinyl chloride resin layer and the interface of the polyolefin resin layer can be improved by providing an adhesive layer of a resin composition containing and in a specific ratio.
Further, in Patent Document 2, a thermoplastic acrylic elastomer and propylene having a specific density are used as a resin composition capable of improving the adhesiveness (heat-resistant adhesiveness) between a soft polyvinyl chloride resin layer and a polyolefin resin layer after heat treatment. A composition containing an elastomer and an ethylene/vinyl acetate copolymer is disclosed, and a laminate using this resin composition as a resin composition for an interlayer adhesive layer between a soft polyvinyl chloride resin layer and a polyolefin resin layer. body is disclosed.

JP 2013-23573 A JP 2018-16759 A

In Patent Document 1 and Patent Document 2, the interlayer adhesive strength is evaluated by peel strength as an adhesive resin composition with a soft polyvinyl chloride resin layer or a polyolefin resin layer. It has been found that the resin composition described in 1. has insufficient peel strength in interlayer adhesion between a polycarbonate resin and a metal plate such as aluminum. In addition, in Patent Document 2, the adhesive strength with the soft polyvinyl chloride resin layer is evaluated by peel strength (90 ° T peel peel test), and the effect of improving the adhesive strength is obtained. Depending on the application, adhesive strength against shear stress applied to the laminate is also required, whereas the adhesive layer using the resin composition described in Patent Document 2 has adhesive strength against such shear stress. found to be inadequate.

The present invention has been made in view of this situation, and its object is to provide a polyvinyl chloride resin layer, a polycarbonate resin layer, and a metal plate such as aluminum with good adhesion, and to provide adhesion against shear stress. An object of the present invention is to provide a resin composition which has good strength and is suitable as a resin composition for interlaminar adhesion, and a molded article, a laminate and a building material using this resin composition.

As a result of intensive studies in view of the above problems, the inventors of the present invention have found that a resin composition containing a polyester elastomer, an ethylene-vinyl acetate copolymer, and a propylene-based elastomer having a specific density in a predetermined ratio. , found that the above problems can be solved, and completed the present invention.
That is, the gist of the present invention is the following [1] to [7].

[1] Contains the following component (A), component (B) and component (C), with 20 to 65% by mass of component (A) and 20 to 65% by mass of component (B) with respect to the total amount of these, A resin composition containing 10 to 50% by mass of component (C).
Component (A): Polyester elastomer Component (B): Propylene elastomer having a density (ASTM D1505) of 855 to 895 kg/m ³ Component (C): Ethylene/vinyl acetate copolymer

[2] The resin composition according to [1], wherein the polyester elastomer of component (A) is an aromatic polyester-polyalkylene glycol block copolymer.

[3] The resin composition according to [2], wherein the polyester elastomer of component (A) is a polybutylene terephthalate-polytetramethylene glycol block copolymer.

[4] A molded article obtained by molding the resin composition according to any one of [1] to [3].

[5] A laminate having a layer containing the resin composition according to any one of [1] to [3] and other layers.

[6] A laminate having a polyvinyl chloride resin layer and an adhesive layer containing the resin composition according to any one of [1] to [3].

[7] A construction material comprising the laminate according to [6] as a component.

According to the present invention, the adhesiveness to the polyvinyl chloride resin layer, the polycarbonate resin layer, and the metal plate such as aluminum is all good, and the adhesiveness to the polyvinyl chloride resin layer against shear stress is particularly good. Provided are a resin composition suitable as a resin composition for the interlayer adhesive layer of No. 1, and a molded article, laminate and building material using the same.
The resin composition of the present invention has a polyvinyl chloride resin layer, a polycarbonate resin layer, a metal plate of aluminum or the like, and is excellent in flexibility, design, and antifouling properties, and is used as an adhesion layer for building materials. It is suitable as a product.

Although the present invention will be described in detail below, the present invention is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention. In addition, in the present invention, when a numerical value or a physical property value is sandwiched before and after the "~", it is used to include the values before and after it.

[Resin composition]
The resin composition of the present invention contains the following component (A), component (B) and component (C). ~65% by mass and 10 to 50% by mass of component (C).
Component (A): Polyester elastomer Component (B): Propylene elastomer having a density (ASTM D1505) of 855 to 895 kg/m ³ Component (C): Ethylene/vinyl acetate copolymer

<Component (A)>
The component (A) polyester elastomer used in the present invention is usually a block copolymer having a crystalline hard segment and a flexible soft segment.

Polyester elastomers include, for example, cyclic polyesters (in the present invention, the term "cyclic polyester" means that the starting material dicarboxylic acid or its alkyl ester contains a dicarboxylic acid or its alkyl ester having a cyclic structure). A block copolymer having a hard segment (hereinafter sometimes referred to as "cyclic polyester unit") and a soft segment made of polyalkylene glycol (hereinafter sometimes referred to as "polyalkylene glycol unit") (hereinafter , Sometimes referred to as a "cyclic polyester-polyalkylene glycol block copolymer".), And a hard segment consisting of a cyclic polyester and a chain aliphatic polyester ("chain aliphatic polyester" in the present invention is a raw material A soft segment consisting of a certain dicarboxylic acid or its alkyl ester which is a dicarboxylic acid or its alkyl ester having only a chain structure (hereinafter sometimes referred to as "chain aliphatic polyester unit"). (hereinafter sometimes referred to as "cyclic polyester-chain aliphatic polyester block copolymer") and the like. Among these, cyclic polyester-polyalkylene glycol block copolymers are preferred.

As the cyclic polyester-polyalkylene glycol block copolymer, for example, a copolymer having a hard segment made of an aromatic polyester (hereinafter sometimes referred to as "aromatic polyester unit") and a polyalkylene glycol unit (hereinafter , It may be referred to as "aromatic polyester-polyalkylene glycol block copolymer".) And a hard segment made of alicyclic polyester (hereinafter sometimes referred to as "alicyclic polyester unit") and polyalkylene and a block copolymer having a glycol unit (hereinafter sometimes referred to as "alicyclic polyester-polyalkylene glycol block copolymer"). Among these, aromatic polyester-polyalkylene glycol block copolymers are preferred.

The aromatic polyester-polyalkylene glycol block copolymer is a known thermoplastic elastomer as described in JP-A-10-130451 and the like, and if it is a polymer containing a polyalkylene glycol unit, each block may be a homopolymer or a copolymer.

The raw material of the aromatic polyester unit will be described in detail below, but it preferably contains polybutylene terephthalate as a hard segment. On the other hand, although the raw material of the polyalkylene glycol unit will also be described in detail below, it is preferable to include a soft segment made from polytetramethylene ether glycol (hereinafter sometimes referred to as "polytetramethylene glycol unit"). .

As the polyester elastomer used in the present invention, a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable, and a polybutylene terephthalate-polytetramethylene glycol block copolymer is particularly preferable.

Further, as the alicyclic polyester-polyalkylene glycol block copolymer, for example, alicyclic dicarboxylic acid ("alicyclic dicarboxylic acid" in the present specification is a cyclic aliphatic hydrocarbon having two carboxyl groups directly It means a bonded compound.), alicyclic diols and polyalkylene glycol as starting materials.

Each block may be a homopolymer or a copolymer as long as the polymer contains a polyalkylene glycol unit. The alicyclic polyester unit preferably contains a hard segment obtained using cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials. The polyalkylene glycol unit of the alicyclic polyester-polyalkylene glycol block copolymer preferably contains a soft segment (polytetramethylene glycol unit) obtained from polytetramethylene ether glycol as a starting material.

Examples of cyclic polyester-chain aliphatic polyester block copolymers include, for example, block copolymers having a hard segment made of an aromatic polyester and a soft segment made of a chain aliphatic polyester (hereinafter referred to as "aromatic polyester-chain may be referred to as "alicyclic polyester block copolymer".) And a block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter, "alicyclic polyester - may be referred to as "chain aliphatic polyester block copolymer").

Among these, aromatic polyester-chain aliphatic polyester block copolymers are preferred. Among the aromatic polyester-chain aliphatic polyester block copolymers, a polybutylene terephthalate-chain aliphatic polyester block copolymer in which the aromatic polyester unit is composed of polybutylene terephthalate is more preferable. Preferred chain aliphatic polyester units are those obtained from chain aliphatic dicarboxylic acids having 4 to 10 carbon atoms, typically sebacic acid and adipic acid, and chain aliphatic diols.

Polyalkylene ether glycol is preferred as the flexible soft segment. Polyalkylene ether glycols include linear and branched fatty acids such as, for example, polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexamethylene glycol. cyclohexanediol condensates and cyclohexanedimethanol condensates homopolymers or copolymers of alicyclic ethers.
Random copolymers in these ether units may also be used. A block copolymer having a polyalkylene glycol unit can also be used.
These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of the polyalkylene glycol contained in the cyclic polyester-polyalkylene glycol block copolymer is preferably 600 to 4,000, more preferably 800 to 2,500, and more preferably 900 to 2,100. It is even more preferable to have
Here, the number average molecular weight of polyalkylene glycol refers to a value calculated by magnetic resonance spectroscopy (NMR).

Only one of these polyalkylene glycols may be contained in the cyclic polyester-polyalkylene glycol block copolymer, or two or more of them having different number average molecular weights or constituent components may be contained.

The method for producing the polyester elastomer is not particularly limited, and may be either a batch polymerization method or a continuous polymerization method. If it is an aromatic polyester-polyalkylene glycol block copolymer, a chain aliphatic and / or alicyclic diol having 1 to 12 carbon atoms, an aromatic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol It can be obtained by condensing an oligomer obtained by an esterification reaction or a transesterification reaction as a raw material.

As the chain aliphatic and/or alicyclic diol having 1 to 12 carbon atoms, those commonly used as starting materials for polyester can be used. Chain aliphatic diols include, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and 1,6-hexene glycol. Among them, 1,4-butylene glycol is preferred.
Alicyclic diols include, for example, 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, with 1,4-cyclohexanedimethanol being preferred.
These chain aliphatic and/or alicyclic diols having 2 to 12 carbon atoms may be used singly or as a mixture of two or more thereof.

As the aromatic dicarboxylic acid or alkyl ester thereof, those commonly used as raw materials for polyesters can be used. .) Alkyl esters, isophthalic acid, phthalic acid, 2,5-norbornenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and lower alkyl esters thereof, etc. is mentioned. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.
One of these aromatic dicarboxylic acids or alkyl esters thereof may be used alone, or two or more thereof may be used in combination.

Examples of polyalkylene ether glycols include, as described above, straight-chain and In addition to branched aliphatic ether glycols, homopolymers or copolymers of alicyclic ethers such as cyclohexanediol condensates and cyclohexanedimethanol condensates can be used.
Moreover, it may be a random copolymer within these ether units.

Preferred among these are linear and branched aliphatic ether glycols such as polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol, polytetramethylene glycol and polyhexamethylene glycol. and more preferred are polymethylene glycol, polyethylene glycol, poly(1,2- and 1,3-)propylene glycol and polytetramethylene glycol, and particularly preferred is polytetramethylene glycol.
These may be used individually by 1 type, and may use 2 or more types together.

Further, when producing an alicyclic polyester-polyalkylene glycol block copolymer, the aromatic dicarboxylic acid or alkyl ester thereof used as a raw material for producing the above-mentioned aromatic polyester-polyalkylene glycol block copolymer An alicyclic dicarboxylic acid or an alkyl ester thereof may be used instead of .

That is, a chain aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an alicyclic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol are used as raw materials, and obtained by an esterification reaction or a transesterification reaction. It can be obtained by polycondensing the obtained oligomer.

As the alicyclic dicarboxylic acid or alkyl ester thereof, those commonly used as starting materials for polyesters can be used, and examples thereof include cyclohexanedicarboxylic acid and its lower alkyl esters, cyclopentanedicarboxylic acid and its lower alkyl esters, and the like. mentioned. Among these, cyclohexanedicarboxylic acid and its lower alkyl ester are preferred, and cyclohexanedicarboxylic acid is particularly preferred.
One of these alicyclic dicarboxylic acids or alkyl esters thereof may be used alone, or two or more thereof may be used in combination.

The content of each of the cyclic polyester unit and the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited. range.

That is, although the lower limit of the content of the cyclic polyester unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited, it is usually 10% by mass or more, preferably 15% by mass or more. Also, the upper limit of the content of the cyclic polyester unit is not limited, but is usually 95% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.

In addition, the lower limit of the content of the polyalkylene glycol unit in the cyclic polyester-polyalkylene glycol block copolymer is not limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more. be. Although the upper limit of the content of the polyalkylene glycol unit is not limited, it is usually 90% by mass or less, preferably 85% by mass or less.

The content of the cyclic polyester unit in the block copolymer having the cyclic polyester unit can be calculated using nuclear magnetic resonance spectroscopy (NMR) based on the chemical shift of the hydrogen atom and its content. can. Similarly, the content of the polyalkylene glycol unit in the block copolymer having a polyalkylene glycol unit is calculated using nuclear magnetic resonance spectroscopy (NMR) based on the chemical shift of its hydrogen atoms and its content. can do.

As the aromatic polyester-polyalkylene glycol block copolymer, a polybutylene terephthalate-polyalkylene glycol block copolymer is preferable because of its high crystallization rate and excellent moldability. The number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 8, still more preferably 2 to 5, and particularly preferably 4.

In addition to the above components, the cyclic polyester-polyalkylene glycol block copolymer, which is represented by the aromatic polyester-polyalkylene glycol block copolymer according to the present invention, contains trifunctional alcohols and tricarboxylic acids and / or A small amount of one or two or more esters may be copolymerized, and a chain aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be introduced as a copolymerization component.

The above cyclic polyester-polyalkylene glycol block copolymer is also available as a commercial product. Examples of such commercial products include "KEYFLEX (registered trademark)" (manufactured by LG Chemical Co., Ltd.), "TEFABLOC (registered trademark)" (manufactured by Mitsubishi Chemical Corporation), and "Pelprene (registered trademark)" (manufactured by Toyobo Co., Ltd.). , “Hytrel (registered trademark)” (manufactured by DuPont) and “Hetroflex (registered trademark)” (manufactured by Hetron).

Polyester elastomers such as cyclic polyester-polyalkylene glycol block copolymers may be used singly or in combination of two or more.

<Component (B)>
The resin composition of the present invention contains, as component (B), a propylene-based elastomer having a density (ASTM D1505) of 855-895 kg/m ³ .
The propylene-based elastomer of component (B) has a propylene content (weight ratio of monomer units derived from propylene to all monomer units) of 50% by mass or more, and a density (ASTM D1505) of 855 to 895 kg/ There is no particular limitation as long as it is ^m3 .

The propylene content of the propylene-based elastomer of component (B) is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. On the other hand, the upper limit of the propylene content of component (B) is not particularly limited, but is usually 90% by mass or less, preferably 88% by mass or less, more preferably 86% by mass or less. In the component (B), when the propylene content is at least the above lower limit, it is preferable from the viewpoint of adhesion to the polypropylene resin, and when it is at most the above upper limit, the ethylene-vinyl acetate copolymer of the component (C). from the viewpoint of compatibility of

From the viewpoint of compatibility with the ethylene/vinyl acetate copolymer, it is preferable that the propylene-based elastomer of component (B) contains other copolymer components in addition to propylene. Such other copolymer components include, for example, ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1- octene and the like. Among these, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like are preferable as other copolymer components, and ethylene and 1-butene are particularly preferable. The other copolymer components listed above may contain only one type, or may contain two or more types.

Component (B) has a density (ASTM D1505) of 855-895 kg/m ³ . When the density of the component (B) is within the above range, the resin composition containing the component (B) is imparted with the effect of maintaining good adhesiveness. The density (ASTM D1505) of component (B) is preferably 860-880 kg/m ³ .

Component (B) preferably has a melt flow rate of 1 to 60 g/10 minutes at 230° C. and a load of 21.2 N (JIS K7210 (1990) from the viewpoint of moldability. Melt flow rate of component (B) is more preferably 2 to 50 g/10 minutes from this point of view.

The propylene-based elastomer of component (B) can be produced by a known polymerization method using a known olefin polymerization catalyst. For example, a polymerization method using a Ziegler-Natta catalyst can be mentioned. A slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be used for this polymerization method, and two or more of these methods may be used in combination.

The propylene-based elastomer of component (B) can be obtained as a commercial product. As applicable commercial products, applicable products can be appropriately selected and used from Mitsui Chemicals, Inc.'s "Tafmer (registered trademark)" series, Exxon Mobil's "Vistamaxx (registered trademark)" series, and the like.

In the resin composition of the present invention, the propylene-based elastomer of component (B) may be used alone or in combination of two or more with different compositions and physical properties.

<Component (C)>
Component (C) used in the resin composition of the present invention is an ethylene/vinyl acetate copolymer. By using the ethylene-vinyl acetate copolymer of the component (C) together with the above-described component (A), the resin composition of the present invention has good adhesion to polyvinyl chloride resin.

The vinyl acetate content in the ethylene/vinyl acetate copolymer in component (C) is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more. On the other hand, it is usually 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. From the viewpoint of adhesion to polyolefin resins, the vinyl acetate content is preferably within the above range.

Here, the vinyl acetate content refers to monomer units derived from vinyl acetate among all the monomer units constituting the ethylene/vinyl acetate copolymer (including "other copolymer components" described later). means the weight percentage of The vinyl acetate content also includes monomer units that form the same chemical structure by modification or the like after polymerization without using a vinyl acetate monomer in the polymerization monomer stage.

In the present invention, the vinyl acetate content of the ethylene-vinyl acetate copolymer of component (C) means a value measured according to JIS K7192 (1999) using a Fourier transform infrared spectrophotometer.

The ethylene/vinyl acetate copolymer of component (C) may contain monomer units derived from other copolymerizable components in addition to ethylene and vinyl acetate. Other copolymerizable components include, but are not limited to, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1- One or more of α-olefins having about 3 to 20 carbon atoms such as decene, (meth)acrylic acid, and (meth)acrylic acid esters can be used. When component (C) contains monomer units derived from other copolymerizable components, the content thereof is 50% by mass or less of the total monomer units constituting the ethylene/vinyl acetate copolymer. is preferably

The melt flow rate (MFR) of the ethylene/vinyl acetate copolymer of component (C) is not limited, but is usually 0.2 to 60 g when measured at 190°C under a load of 21.2 N according to JIS K7210 (1999). /10 min, preferably 1 to 35 g/10 min, more preferably 2 to 30 g/10 min. When the MFR is equal to or less than the above upper limit, the extrusion moldability of the resin composition obtained tends to be good, and furthermore, the mechanical strength when formed into a laminate tends to be improved. When the MFR is at least the above lower limit, the fluidity tends to be good, so the moldability of the resulting resin composition tends to be good.

The method for producing the ethylene/vinyl acetate copolymer of component (C) is not particularly limited, but conventionally known production methods such as solution polymerization, latex polymerization and high-pressure radical polymerization can be mentioned. In particular, in order to produce an ethylene/vinyl acetate copolymer having a vinyl acetate content within the range of component (C), solution polymerization is preferred. Specific conditions for producing the ethylene/vinyl acetate copolymer of component (C) by solution polymerization are not limited, but usually ethylene and vinyl acetate are used as essential raw materials, tert-butanol or the like is used as a solvent, Using a radical initiator such as an organic peroxide or an azo compound, at a temperature of 50-150° C., preferably 55-70° C., 10-70 MPa (100-700 bar), preferably 30-40 MPa (300-400 bar) ) under pressure. Such a production method is described, for example, in JP-A-1-101304, JP-A-7-33829, European Patent Application Publication No. A0341499, European Patent Application Publication No. A0510478, etc. .

The ethylene/vinyl acetate copolymer of component (C) is also available as a commercial product. Commercially available products, for example, "LEVAPREN (registered trademark)" manufactured by LANXESS, "EVAFLEX (registered trademark)" manufactured by DuPont Mitsui Polychemical Co., Ltd., etc., can be selected and used. .

In the resin composition of the present invention, the ethylene/vinyl acetate copolymer of component (C) may be used alone or in combination of two or more with different compositions and physical properties.

<Other ingredients>
The resin composition of the present invention may contain resin components other than the components (A), (B), and (C) (hereinafter referred to as "other resins"), as long as the effects of the present invention are not significantly impaired. ), various additives, fillers, and the like can be blended. Other resins may be used alone, or two or more of them may be used in any combination and ratio.

Specific examples of other resins include, for example, polyolefin resins (excluding those contained in component (B)); polyphenylene ether resins; polyamide resins such as nylon 6, nylon 66 and nylon 11; polyethylene terephthalate; polyester resins such as polybutylene terephthalate (excluding those contained in component (A)); (meth)acrylic resins such as polymethyl methacrylate resins; styrene resins such as polystyrene; A plastic elastomer and the like can be mentioned.

Various additives and the like can be added to the resin composition of the present invention as long as they do not significantly impair the effects of the present invention. Additives include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, anti-aging agents, nucleating agents, plasticizers, impact modifiers, compatibilizers, antifoaming agents, thickeners, Cross-linking agents, surfactants, lubricants, release agents, antiblocking agents, processing aids, antistatic agents, flame retardants, auxiliary flame retardants, colorants and the like. These additives may be used alone, or two or more of them may be used in any combination and ratio.

Examples of heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.

Flame retardants are roughly classified into halogen flame retardants and non-halogen flame retardants, and non-halogen flame retardants are preferable from an environmental point of view. Non-halogen flame retardants include phosphorus flame retardants, hydrated metal compound (aluminum hydroxide, magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine, guanidine) flame retardants and inorganic compounds (borate, molybdenum compound) flame retardants and the like.

The resin composition of the present invention preferably contains an antiblocking agent as an additive. Addition of an anti-blocking agent tends to improve blocking resistance between pellets during the process of producing pellets made of the resin composition of the present invention, subsequent storage, transportation, and the like. Examples of antiblocking agents include polyolefin fine powder, polyethylene wax and dispersions thereof.

Fillers are roughly classified into organic fillers and inorganic fillers. Examples of organic fillers include naturally derived polymers such as starch, cellulose fine particles, wood flour, bean curd refuse, rice husks, bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, and carbon. Black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, carbon fibers and the like.

<Combination amount>
In the resin composition of the present invention, the content of component (A) is 20 to 65% by mass with respect to the total amount of component (A), component (B) and component (C). A content of component (A) of 20% by mass or more relative to the total amount of component (A), component (B) and component (C) is preferable from the viewpoint of adhesion to polyvinyl chloride resin. A content of component (A) of 65% by mass or less is preferable from the viewpoint of adhesion to the polycarbonate resin. From these viewpoints, the content of component (A) is preferably 23% by mass or more, more preferably 25% by mass or more, and is preferably 60% by mass or less, more preferably 55% by mass. It is below.

In the resin composition of the present invention, the content of component (B) is 20 to 65% by mass with respect to the total amount of component (A), component (B) and component (C). When the content of component (B) is 25% by mass or more, it is preferable from the viewpoint of compatibility and adhesiveness with the polyolefin resin. It is preferable from the viewpoint of adhesion to vinyl resin. From these viewpoints, the content of component (B) is preferably 27% by mass or more, more preferably 29% by mass or more, while preferably 50% by weight or less, more preferably 45% by mass. It is below.

In the resin composition of the present invention, the content of component (C) is 10 to 50% by mass with respect to the total amount of component (A), component (B) and component (C). A content of component (C) of 10% by mass or more is preferable from the viewpoint of compatibility between components (A) and (B), while a content of component (C) of 50% by mass or less is preferable. , from the viewpoint of adhesion to polyolefin resins. From these viewpoints, the content of component (C) is preferably 13% by mass or more, more preferably 15% by mass or more, and is preferably 47% by mass or less, more preferably 45% by mass. It is below.

When the resin composition of the present invention contains the other resins described above, the content is not limited, but is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass in the resin composition. . If the content of the other resin exceeds the above upper limit, the adhesiveness of the obtained resin composition to a polyvinyl chloride resin, a polycarbonate resin, or a metal plate such as aluminum may be insufficient.

When the resin composition of the present invention contains the above-described additive, the content is not limited, but is usually 0.01 to 10% by mass, preferably 0.2 to 5% by mass in the resin composition. If the content of the additive exceeds the above upper limit, the adhesiveness of the obtained resin composition to the polyvinyl chloride resin may be insufficient. When the resin composition of the present invention is used as a masterbatch, these additives can be contained at a concentration of 2 to 50 times, preferably 3 to 30 times the above-described content.

<Melt flow rate (MFR)>
The melt flow rate (MFR) of the resin composition of the present invention is not limited, but according to JIS K7210 (1999), the value measured at 190 ° C. and a load of 21.2 N is usually 0.2 to 60 g / 10 minutes, preferably The range of 1 to 30 g/10 minutes, more preferably 2 to 25 g/10 minutes is suitable. When the MFR is equal to or less than the above upper limit, the extrusion moldability of the resin composition tends to be good, and furthermore, the mechanical strength of the laminate tends to be improved. When the MFR is at least the above lower limit, the fluidity is good, and the moldability of the resin composition tends to be improved.

<Method for producing resin composition>
The resin composition of the present invention can be obtained by mixing each component described above in a predetermined ratio. The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, a composition in which each component is uniformly dispersed can be obtained by mixing the raw material components described above at the same time or in an arbitrary order. For more uniform mixing and dispersion, it is preferable to melt-mix predetermined amounts of the raw material components. For example, the raw material components of the resin composition of the present invention are mixed in an arbitrary order and then heated. All raw material components may be mixed while being melted sequentially, or each raw material may be appropriately blended (dry blended) and melt-mixed at the time of molding for producing the desired molded body.

The mixing method and mixing conditions are not particularly limited as long as each raw material component is uniformly mixed. However, a method of melt-kneading with a continuous kneader such as a single-screw extruder or a twin-screw extruder and a batch kneader such as a mill roll, a Banbury mixer, or a pressure kneader is preferred. The production conditions for producing the resin composition by these methods are not limited, and can be appropriately set to well-known conditions. The temperature during melt-mixing may be a temperature at which at least one of the raw material components is in a molten state, but usually a temperature at which all the components used are melted is selected, and the temperature is generally 150 to 250°C.

[Molded body]
The molded article obtained from the resin composition of the present invention is not limited, and can be various extrusion molded articles and injection molded articles. There are no particular restrictions on the method of manufacturing the molded body, and specific examples include various molding methods such as injection molding, blow molding, extrusion molding, and inflation molding, and vacuum molding and air pressure molding using sheets obtained by these molding methods. Secondary forming methods such as molding, vacuum pressure forming and the like are included.
Further, the resin composition of the present invention can be used alone to form a molded article such as a single layer sheet. , it is more effective to use the resin composition as one layer as a laminate.

[Laminate]
A laminate using the resin composition of the present invention is a laminate obtained by laminating two or three layers or more including a layer made of the resin composition of the present invention (hereinafter sometimes referred to as a resin composition layer). . The shape of the laminate of the present invention is not limited, and may be any shape such as a planar shape such as a film, a sheet, or a plate, a pipe shape, a bag shape, or an irregular shape. The material constituting the layer other than the resin composition layer (hereinafter sometimes referred to as another layer) is not limited, and may be a metal layer as well as a resin layer. The material of the resin layer constituting the laminate is not limited, and examples thereof include those exemplified as other resins that can be used in the resin composition of the present invention. Moreover, the resin layer constituting the laminate may contain additives that can be used in the resin composition of the present invention.

Among these, a laminate having a layer composed of the resin composition of the present invention as an adhesive layer and a polyvinyl chloride resin layer and/or a polycarbonate resin and/or a metal plate such as aluminum, which will be described later, is particularly preferable. Although the layer structure of the laminate in this case is not limited, it is preferably a laminate in which the polyvinyl chloride resin layer and the adhesive layer, and/or the adhesive layer, the polycarbonate resin layer, and the metal plate layer are in contact with each other. .

When the laminate of the present invention is used for building materials such as wallpaper and decorative sheets, a polycarbonate resin layer or an aluminum layer that causes less surface contamination and is suitable in terms of hygiene and environment is placed on the outer surface side, and the laminate of the present invention is used. It is preferable to adopt a structure in which an adhesive layer made of a resin composition is used as an intermediate layer and a polyvinyl chloride resin layer having good flexibility and moldability is used as an inner layer. In this case, the polyvinyl chloride resin layer side is provided with an adhesive layer, a release layer, and the like to form a multi-layer structure, and the release layer can be peeled off before use.

<Polyvinyl chloride resin layer>
The polyvinyl chloride resin layer forming the laminate contains at least polyvinyl chloride resin. Although the polyvinyl chloride resin constituting the polyvinyl chloride resin layer is not limited, examples thereof include homopolymers and copolymers of vinyl chloride. Monomers copolymerizable with vinyl chloride are not limited, but examples thereof include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester, methacrylic acid or its ester, and vinylidene chloride. It may also be a partially crosslinked resin. Polymer blends of polyvinyl chloride resins, for example, polymer blends of polyvinyl chloride resin and polyvinylidene chloride may also be used. Among these, vinyl chloride homopolymers are preferable as the polyvinyl chloride resin used for the polyvinyl chloride resin layer.

The average degree of polymerization of the polyvinyl chloride resin used for the polyvinyl chloride resin layer is not limited, but it is usually from 500 to 6,000, preferably from 800 to 3,000. Although the reduced viscosity (K value) of the polyvinyl chloride resin is not limited, it is usually 50 to 110, preferably 60 to 90 as a value based on JIS K7367-2.

The method for producing the polyvinyl chloride resin is not limited, and for example, it can be produced by a suspension polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like. Also, plastisol or water-based latex in which fine particles of polyvinyl chloride resin are dispersed in an organic medium may be used.

The polyvinyl chloride resin used for the polyvinyl chloride resin layer preferably contains a plasticizer.
The plasticizer used in the polyvinyl chloride resin is not particularly limited, and one or more known plasticizers can be used.

When the plasticizer is used, its blending amount is not limited, but it is usually 1 to 150 parts by mass, preferably 15 to 120 parts by mass, more preferably 20 to 100 parts by mass, per 100 parts by mass of the polyvinyl chloride resin. When the blending amount of the plasticizer is at least the above lower limit, the laminate of the present invention tends to have good flexibility. On the other hand, when the blending amount of the plasticizer is equal to or less than the above upper limit, bleeding out of the plasticizer from the laminate of the present invention is suppressed, and moldability is improved.

The polyvinyl chloride resin used for the polyvinyl chloride resin layer may contain a stabilizer. The stabilizer used for the polyvinyl chloride resin is not limited, but can be appropriately selected from known stabilizers for polyvinyl chloride resin. Examples include tribasic lead sulfate, dibasic lead phthalate, Lead silicate, lead orthosilicate-silica gel coprecipitate, dibasic lead stearate, cadmium-barium stabilizer, barium-zinc stabilizer, calcium-zinc stabilizer, tin stabilizer, and hydrotal Stabilizers containing inorganic salts such as magnesium, aluminum, silicon, etc. as a main component. These stabilizers may be used alone or in combination of two or more compounds.

When the stabilizer is used, its blending amount is not limited, but it is usually 1 to 30 parts by mass, preferably 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, per 100 parts by mass of the polyvinyl chloride resin. When the stabilizer is blended within the above range, the thermal stability and moldability tend to be improved.

<Method for manufacturing laminate>
The method for producing the laminate of the present invention is not limited, and conventionally known various methods can be employed. In particular, since the resin composition of the present invention has good adhesiveness, a laminate having good adhesiveness can be obtained by the following molding method without dry lamination using an organic solvent. . Specifically, for example, by a co-extrusion method in which individual molten resins melted in an extruder are supplied to a multi-layer die and laminated and molded in the die, a blown film, a T-die film, a sheet, a pipe, etc. and co-injection molding in which melted individual resins are injected into the same mold with a time lag. Further, extrusion lamination molding can also be employed in which a resin film constituting any one of the layers is molded in advance and the other layers are melt-extruded thereon. Furthermore, it is also possible to form a laminate in advance by forming resin films constituting each layer in advance and applying heat to fuse these layers.

Moreover, the laminate of the present invention can also be made into a stretched laminate by stretching the laminate after obtaining the laminate by the molding method as described above. The stretched laminate may be heat-set, or may be used as a product without heat-setting. When the heat setting is not performed, the stretched laminate can be used as a shrink film because the stress is released by heating the stretched laminate and the laminate shrinks. Furthermore, these can be made into draw-formed containers or the like through secondary processing such as vacuum forming and pressure forming.

The thickness (total thickness) of the laminate of the present invention is not limited, and can be arbitrarily set depending on the layer structure, application, shape of the final product, required physical properties, etc., but is usually 30 to 500 μm, and It is preferably 40 to 400 μm, particularly preferably 50 to 300 μm. In addition, in the examples described later, the thickness of the laminate is set to be greater than the above upper limit for the evaluation of the adhesive strength.

The thickness of the resin composition layer (adhesive layer) in the laminate of the present invention is not limited, and can be arbitrarily set depending on the layer structure, application, shape of the final product, required physical properties, etc. It is usually 1% or more, preferably 5% or more, and usually 20% or less, preferably 10% or less. When the thickness of the resin composition layer is at least the lower limit, the adhesiveness tends to be good, and when the thickness is at most the upper limit, the film strength tends to improve.

[Use]
Since the resin composition of the present invention has good adhesiveness to polyvinyl chloride resin, polycarbonate resin, metal plates such as aluminum, etc., the obtained laminate is suitably used as a building material such as wallpaper and decorative sheet. In addition, it can be widely applied to protective films for various molded products, antifouling films, packaging materials, and the like. Among these, it can be preferably used as wallpaper. When the laminate of the present invention is used as wallpaper, an adhesive layer, a substrate layer, an antifouling layer, a release layer, and the like may be further provided. Also, physical treatment such as embossing may be performed, and good interlayer adhesion can be maintained in this case as well.

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention. It may be a range defined by the value of the example or a combination of the values of the examples.

[raw materials used]
Raw materials used in the following examples and comparative examples are as follows.

<Component (A): Polyester elastomer>
(A-1) Polyester-polyalkylene glycol block copolymer LG Chemical Co., Ltd. "KEYFLEX (registered trademark) BT1028D"
Number average molecular weight of polytetramethylene glycol: 1,700
Content of polybutylene terephthalate unit: 27% by mass
Content of polytetramethylene glycol unit: 73% by mass
Melting point: 155°C
MFR: 25g/10min (230°C, 21.2N)
Specific gravity: 1.05
Duro A hardness: 88
(A-2) Polyester-polyalkylene glycol block copolymer "Hetroflex (registered trademark) H25DMG" manufactured by Hetron Co., Ltd.
Number average molecular weight of polytetramethylene glycol: 1,800
Content of polybutylene terephthalate unit: 20% by mass
Content of polytetramethylene glycol unit: 80% by mass
Melting point: 168°C
MFR: 18g/10min (230°C, 21.2N)
Specific gravity: 1.06
Duro A hardness: 82
(A-3) Unsaturated carboxylic acid-modified polyester-based elastomer "Modic (registered trademark) GQ131" manufactured by Mitsubishi Chemical Corporation
Melting point: 145°C
MFR: 35g/10min (230°C, 21.2N)
Specific gravity: 1.06
Duro A hardness: 76

<Component (B): Propylene-based elastomer>
(B-1)
"Tafmer (registered trademark) PN-2060" manufactured by Mitsui Chemicals, Inc.
Density (ASTM D1505): 868 kg/ ^m3
MFR: 6.0g/10min (230°C, 21.2N)
Melting point: 160°C

<Component (C): Ethylene-Vinyl Acetate Copolymer>
(C-1)
“Evaflex (registered trademark) EV150” manufactured by Mitsui DuPont Polychemicals Co., Ltd.
Vinyl acetate content: 33% by mass
MFR: 30.0g/10min (190°C, 21.2N)
Density: 0.960g/ ^cm3
Melting point: 61°C

<Component (X): Other elastomer>
(X-1) Acrylic thermoplastic elastomer “Clarity (registered trademark) LA4285” manufactured by Kuraray Co., Ltd.
Hard segment: polymer block of methyl methacrylate (50% by mass)
Soft segment: polymer block of n-butyl acrylate (50% by mass)
Weight average molecular weight (Mw): 58,000
Molecular weight distribution (Mw/Mn): 1.13
Glass transition temperature (Tg): 141°C, 29°C
MFR: 1.5g/10min (190°C, 21.2N)
Specific gravity: 1.11
Duro A hardness: 46

[Examples 1 to 3 and Comparative Example 1]
<Preparation of sample for adhesion evaluation with aluminum and polycarbonate resin>
Each raw material component was used in the mixing ratio shown in Table 1, and kneaded at 180 to 200° C. using a micro kneader. An adhesive resin sheet having a thickness of 2 mm was prepared from the kneaded material, and an aluminum plate or a polycarbonate resin plate was laminated on the adhesive resin sheet at 200° C. to prepare an evaluation sample.

<Sample preparation for adhesion evaluation with polyvinyl chloride resin>
Each raw material component was used in the mixing ratio shown in Table 1, and an adhesive resin sheet having a thickness of 1 mm was molded using a press. An adhesive resin sheet prepared between a polypropylene sheet with a thickness of 1 mm and a polyvinyl chloride sheet with a thickness of 1 mm was superimposed with a width of 5 mm and adhered with a press to prepare a sample for evaluation.

[Method for evaluating adhesive strength]
<Evaluation of sample for evaluation of adhesion to aluminum and polycarbonate resin>
The samples for evaluation of adhesion to the aluminum plate or polycarbonate resin plate of Examples 1 to 3 and Comparative Example 1 were cut into 15 mm widths, and the space between the adhesive resin sheet at one end and the aluminum plate or polycarbonate resin plate was peeled off with a cutter knife. .
The 90° peel strength was measured by pulling the adhesive resin sheet at 50 mm/min while maintaining the peeled adhesive resin sheet and the aluminum plate or polycarbonate resin plate at 90°.
Measurements were performed at 23°C.

<Evaluation of sample for evaluation of adhesion with polyvinyl chloride resin>
The samples for adhesion evaluation with the polyvinyl chloride resin of Examples 1 to 3 and Comparative Example 1 were cut to a width of 15 mm, and the polypropylene sheet was gripped on one side of the tensile tester, and the polyvinyl chloride sheet was gripped on the other side at 50 mm/min. The shear peel strength was measured by pulling with
Measurements were performed at 23°C.

The peel strengths of the 90° peel test and the shear peel test are shown in Table 1 as adhesive strength.
Among the evaluation results in Table 1, "against AL", "against PC", and "against PVC" are the aluminum plate, polycarbonate resin plate, polyvinyl chloride sheet and resin composition layer (adhesive layer), respectively. means adhesive strength.

From Table-1, those using the resin composition of the present invention containing component (A), component (B), and component (C) have adhesive strength to aluminum, to polycarbonate resin, and to polyvinyl chloride resin is good.

On the other hand, in Comparative Example 1 using the component (X-1), which is an acrylic thermoplastic elastomer, instead of the component (A), in an atmosphere of 23 ° C., It did not exhibit good adhesive strength with vinyl resin either.

Claims (5)

The following component (A), component (B) and component (C) are included, with 20 to 65% by mass of component (A), 20 to 65% by mass of component (B), and 20 to 65% by mass of component (C) ) containing 10 to 50% by mass.
Component (A): polybutylene terephthalate-polytetramethylene glycol block copolymer
Component (B): A propylene-based elastomer having a density (ASTM D1505) of 855 to 895 kg/m ³ and a propylene content of 50% by mass or more and 90% by mass or less Component (C): Ethylene/vinyl acetate copolymer A molded article obtained by molding the resin composition according to claim 1 . A laminate comprising a layer containing the resin composition according to claim 1 and other layers. A laminate having a polyvinyl chloride resin layer and an adhesive layer containing the resin composition according to claim 1 . A building material comprising the laminate according to claim 4 as a component.