JP2018016759A - Resin composition, laminate and building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable as a resin for adhesive layer which has good adhesiveness between a polyvinyl chloride resin layer, and a polyolefin resin layer and an ethylene-vinyl acetate copolymer saponified matter layer, can be melt-molded and thermally bonded without essentially using an organic solvent-based adhesive, and has good adhesiveness with the resin layer even under high temperature environment.SOLUTION: A resin composition contains the following component (A), component (B) and component (C), and contains 20-65 wt.% of the component (A), 25-55 wt.% of the component (B) and 10-50 wt.% of the component (C) to a total amount thereof. The component (A) is an acrylic thermoplastic elastomer. The component (B) is a propylene elastomer having a density (ASTM D1505) of 855-895 kg/m. The component (C) is an ethylene-vinyl acetate copolymer.SELECTED DRAWING: None

Description

The present invention relates to a resin composition having good adhesion to a polyvinyl chloride resin and a polyolefin resin, and a laminate and a building material having a layer containing the resin composition.
The resin composition of the present invention is suitable for making a laminate having no polyvinyl chloride resin layer and a polyolefin resin layer by co-extrusion or extrusion lamination, etc. It is possible to provide a laminate in which the adhesion between the layer containing the product, the polyvinyl chloride resin layer, and the polyolefin resin layer is good even after the heat treatment.

  As a base material for building materials such as wallpaper and a decorative sheet, a soft polyvinyl chloride resin base material is frequently used because it is flexible and has good moldability. In addition, as a building material made of soft polyvinyl chloride resin, an embossed or foamed material is used in applications where improvement in touch and design are required. Soft polyvinyl chloride resin is also used for automobile interior parts because it has excellent flexibility and feel and is low in cost. As demands for weight reduction increase, it is required to reduce the weight by making a layered structure of a soft polyvinyl chloride resin component with a polyolefin resin having a lower specific gravity.

  However, a soft polyvinyl chloride resin usually contains a large amount of plasticizer with respect to the resin, and it is inevitable that this plasticizer bleeds out from the surface of the building material over time. The bleed-out of the plasticizer from the soft polyvinyl chloride resin not only pollutes the surface of the building material itself, reduces the flexibility and causes cracks, but is not preferable in terms of hygiene and environment. In particular, a building material subjected to embossing or foaming has irregularities formed on the surface or is porous, so that the bleed-out of the plasticizer becomes more prominent.

  As a means for suppressing the plasticizer from bleeding out from the building material made of soft polyvinyl chloride resin, a method of covering the surface with another resin can be mentioned. In particular, polyolefin resins such as polyethylene, polypropylene, and ethylene / α-olefin copolymers have good chemical stability and do not contain a large amount of plasticizer, so there is little surface contamination, and hygiene and environmental aspects. Is also suitable.

  As a method for laminating the polyolefin resin layer on the surface of the soft polyvinyl chloride resin layer, a dry laminating method is generally used. In the dry laminating method, an organic solvent is usually used to bond the layers. However, the use of the organic solvent in the manufacturing process is not preferable because there is a concern about the influence on the natural environment. For this reason, it is strongly desired to manufacture by a molding method that does not use an organic solvent (a melt molding method such as a coextrusion method or an extrusion coating method, or a thermal bonding method).

  As a technology to meet this demand, Patent Document 1 discloses an outer layer made of a soft polyvinyl chloride resin, an ethylene / vinyl acetate copolymer having a high vinyl acetate content, and an ethylene / vinyl acetate copolymer having a low vinyl acetate content. A laminate comprising an intermediate layer containing a specific amount of coalescence and a polyolefin resin layer is disclosed.

JP 2013-23573 A

As a result of further studies on the technique disclosed in Patent Document 1, the present inventor has found that the adhesiveness (heat resistant adhesiveness) after heat treatment is insufficient when heat treatment is performed. It was.
That is, at present, a soft polyvinyl chloride resin layer and a polyolefin resin layer can be integrated by a melt molding method or a thermal bonding method without using an organic solvent as an essential component, and good interlayer adhesion can be obtained. In addition, no adhesive resin has yet been found that exhibits good interlayer adhesion even after heat treatment.

  The present invention has been made in view of such a situation, and the problem is that the adhesion between the polyvinyl chloride resin layer and the polyolefin resin layer or the saponified ethylene / vinyl acetate copolymer layer is the same before and after the heat treatment. Both are good, can be bonded by melt molding method or thermal bonding method without using organic solvent-based adhesive as an essential, and good adhesion with the above resin layer even in high temperature atmosphere The object is to provide a resin composition suitable as a resin for an adhesive layer. In addition, the present invention has a polyvinyl chloride resin layer and a polyolefin resin layer, is excellent in flexibility, design properties, antifouling properties, and as an adhesive layer of a building material in which bleedout of a plasticizer is suppressed, Another object of the present invention is to provide a resin composition that has a polyvinyl chloride resin layer and a polyolefin resin layer, and is suitable as an adhesive layer for automotive parts having excellent flexibility, lightness, touch, and cost.

As a result of intensive studies in view of the above problems, the present inventors have determined that an acrylic thermoplastic elastomer, an ethylene / vinyl acetate copolymer having a specific vinyl acetate content, and a propylene-based elastomer having a specific density are predetermined. The present inventors have found that the above-mentioned problems can be solved by using a resin composition contained in a proportion, and have completed the present invention.
That is, the gist of the present invention is the following [1] to [9].

[1] The following component (A), component (B) and component (C) are included, component (A) is 20 to 65% by weight, component (B) is 25 to 55% by weight based on the total amount thereof, A resin composition containing 10 to 50% by weight of component (C).
Component (A): Acrylic thermoplastic elastomer component (B): Propylene elastomer component (C): Density (ASTM D1505) of 855 to 895 kg / m ³ : Ethylene / vinyl acetate copolymer

[2] The resin composition according to [1], wherein the component (A) has a hard segment composed of a polymer of methyl methacrylate and a soft segment composed of a polymer of n-butyl acrylate.

[3] The following component (D) is included, and the content thereof is 0.5 to 5 parts by weight with respect to 100 parts by weight in total of the component (A), the component (B), and the component (C). ] Or the resin composition as described in [2].
Component (D): Maleic anhydride modified polyolefin

[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 another layer.

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

[7] The laminate according to [6], wherein the polyvinyl chloride resin layer and the adhesive layer and / or the adhesive layer and the polyolefin resin layer are in contact with each other.

[8] The laminate according to [6] or [7], wherein the polyolefin resin layer is a polypropylene resin layer.

[9] A building material comprising the laminate according to any one of [6] to [8] as a constituent.

  According to the present invention, the adhesion between the polyvinyl chloride resin layer and the polyolefin resin layer is good both before and after the heat treatment, and it can be bonded by a melt molding method or a heat bonding method without using an organic solvent-based adhesive. A resin composition suitable as an adhesive layer resin that can be used, and a laminate using the same are provided. In addition, according to the present invention, the adhesive layer of a building material having a polyvinyl chloride resin layer and a polyolefin resin layer, excellent in flexibility, design properties, and antifouling properties, and suppressed in bleed out of a plasticizer. As such, a suitable resin composition is provided.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this invention, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

[Resin composition]
The resin composition of the present invention includes the following component (A), component (B) and component (C), and the component (A) is 20 to 65% by weight and the component (B) is 25 with respect to the total amount thereof. -55 weight% and a component (C) are contained 10-50 weight%.
Component (A): Acrylic thermoplastic elastomer component (B): Propylene elastomer component (C): Density (ASTM D1505) of 855 to 895 kg / m ³ : Ethylene / vinyl acetate copolymer

<Component (A)>
The component (A) used for the resin composition of the present invention is an acrylic thermoplastic elastomer. The acrylic thermoplastic elastomer has an effect of improving the adhesiveness of the polyvinyl chloride resin and the polyolefin resin in a high temperature atmosphere.

  The acrylic thermoplastic elastomer of component (A) is usually a block copolymer having a hard segment having a glass transition temperature of normal temperature (23 ° C.) or higher and a soft segment having flexibility.

  In component (A), the glass transition temperature based on the hard segment is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C. or higher, while preferably 200 ° C. or lower, More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less. The glass transition temperature is preferably in the above range from the viewpoints of heat resistance, moldability, and the like. In the present invention, the glass transition temperature of the component (A) is measured by a dynamic viscoelasticity measuring device when the test piece is heated under the conditions of a temperature range of −100 to 280 ° C., a heating rate of 5 ° C./min, and a frequency of 10 Hz. Is the peak temperature of the loss tangent (tan δ) observed in FIG. In a thermoplastic elastomer having a plurality of blocks, a plurality of loss tangent peaks are usually observed. In this case, the low temperature side peak is derived from the soft segment, and the high temperature side peak is derived from the hard segment. Is.

  In the component (A), the lower limit of the hardness of the component (A) is preferably 60 or more and more preferably 70 or more in terms of the durometer A hardness because of the flexibility based on the soft segment. Is preferably 60 or less, more preferably 50 or less in terms of duro A hardness. When the hardness is in the above range, it is preferable from the viewpoint of heat-resistant adhesion to the polyvinyl chloride resin. In addition, the duro A hardness of a component (A) is a value measured based on ISO7619.

  The hard segment of component (A) is preferably a polymer block obtained from one or more of the following (meth) acrylic monomers. Such (meth) acrylic monomers include methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, ( Examples include hydroxypropyl methacrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Among these, methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferable, and methyl methacrylate is particularly preferable. That is, the hard segment of component (A) is particularly preferably a methyl methacrylate polymer block.

  The soft segment of component (A) is preferably a polymer block obtained from one or more of the following (meth) acrylic monomers. Examples of such (meth) acrylic monomers include n-propyl (meth) acrylate, n-butyl (meth) acrylate, (sec) -secbutyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include ethylhexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, and phenylethyl (meth) acrylate. Among these, n-propyl acrylate, n-butyl acrylate, -secbutyl acrylate, n-hexyl acrylate, ethyl hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, phenylethyl acrylate, etc. Preferably, n-butyl acrylate is particularly preferable. That is, the soft segment of component (A) is particularly preferably a polymer block of n-butyl acrylate.

  The acrylic thermoplastic elastomer of component (A) preferably has a hard segment to soft segment weight ratio ([hard segment weight] / [soft segment weight]) of 10/90 to 70/30, 15 It is more preferable that it is / 85-60 / 40.

  The weight average molecular weight (Mw) of the component (A) is preferably 20,000 or more, more preferably 30,000 or more, still more preferably 40,000 or more, while 600,000 or less. Preferably, it is 400,000 or less, more preferably 200,000 or less. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component (A), that is, the molecular weight distribution (Mw / Mn) is usually 1.1 to 5.0, preferably 1.1 to 3.0. It is.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by the gel permeation chromatography method (GPC method) under the following conditions.
Device: HLC-8120 manufactured by Tosoh Corporation
Column: Inertsil WF300
Solvent: Tetrahydrofuran Calibration: Polystyrene

  The acrylic thermoplastic elastomer of component (A) can be obtained as a commercial product. For example, it can be selected from the Kuraray Clarity (registered trademark) series, Kaneka Nabster (registered trademark) series, or the like.

  In the resin composition of the present invention, only one type of acrylic thermoplastic elastomer of component (A) may be used, or two or more types having different hard segment or soft segment compositions and physical properties may be used in combination. Good.

<Component (B)>
The resin composition of this invention contains the propylene-type elastomer whose density (ASTM D1505) is 855-895 kg / m < ³ > as a component (B). 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 weight or more, and a density (ASTM D1505) of 855 to 895 kg / as long as the m ³ is not particularly limited. By including the component (B) in addition to the component (A) and the component (C), when a polypropylene resin is used as the polyolefin resin layer to be described later, the heat resistant adhesiveness tends to be particularly improved.

  The propylene content of the propylene elastomer of component (B) is 50% by weight or more, preferably 55% by weight or more, more preferably 60% by weight 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 weight or less, preferably 88% by weight or less, and more preferably 86% by weight or less. In component (B), when the propylene content is not less than the above lower limit value, it is preferable from the viewpoint of adhesiveness to polypropylene resin, and when it is not more than the above upper limit value, the ethylene / vinyl acetate copolymer of component (C) From the standpoint of compatibility.

  In view of compatibility with the ethylene / vinyl acetate copolymer, the propylene-based elastomer of the component (B) preferably contains other copolymer components in addition to propylene. Examples of such other copolymerization components include ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1- Examples include octene. Among these, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like are preferable, and ethylene and 1-butene are particularly preferable. The other copolymerization component mentioned above may contain only 1 type, or may contain 2 or more types.

The density of component (B) (ASTM D1505) is 855 to 895 kg / m ³ . When the density of the component (B) is in the above range, the resin composition containing the component (B) is imparted with an effect of maintaining good adhesion with the polyolefin resin. The density of component (B) (ASTM D1505) is preferably 860 to 880 kg / m ³ .

  Component (B) is preferably a melt flow rate at 230 ° C. under a load of 21.2 N (JIS K7210 (1990) is 1 to 60 g / 10 min from the viewpoint of moldability. Melt flow rate of component (B) From this viewpoint, it is more preferably 2 to 50 g / 10 min.

  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. As this polymerization method, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be used, and these may be produced by combining two or more thereof.

  The propylene-based elastomer of component (B) can be obtained as a commercial product. Applicable commercial products can be appropriately selected from the “Tafmer (registered trademark)” series manufactured by Mitsui Chemicals, the “Vistamaxx (registered trademark)” series manufactured by ExxonMobil, and the like.

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

<Ingredient (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 component (A) described above, the resin composition of the present invention has good adhesion to the polyvinyl chloride resin.

  The vinyl acetate content in the ethylene / vinyl acetate copolymer in the component (C) is usually 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more, and further preferably 25% by weight or more. On the other hand, it is usually 99% by weight or less, preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight or less. It is preferable from a viewpoint of the adhesiveness with respect to polyolefin resin that vinyl acetate content is the said range.

  Here, the vinyl acetate content is a monomer unit derived from vinyl acetate among all the monomer units constituting the ethylene / vinyl acetate copolymer (including “other copolymerization components” described later). It means the weight ratio. The vinyl acetate content includes monomer units that form the same chemical structure by modification 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 are not limited, and examples thereof include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-octene, 1 type or 2 types or more, such as C3-C20 alpha olefins, such as a decene, (meth) acrylic acid, (meth) acrylic acid ester, etc. are mentioned. When the component (C) contains monomer units derived from other copolymerizable components, the content is 50% by weight or less of the total monomer units constituting the ethylene / vinyl acetate copolymer. It is preferable that

  The melt flow rate (MFR) of the ethylene / vinyl acetate copolymer of component (C) is not limited, but the value measured at 190 ° C. and a load of 21.2 N is usually 0.2 to 60 g in accordance with JIS K7210 (1999). / 10 minutes, preferably 1 to 35 g / 10 minutes, more preferably 2 to 30 g / 10 minutes. When the MFR is not more than the above upper limit value, the extrudability of the resulting resin composition tends to be good, and the mechanical strength in the case of a laminate tends to be improved. If the MFR is not less than the above lower limit value, the fluidity tends to be good, and the moldability of the resulting resin composition tends to be good.

  Although the manufacturing method of the component (C) ethylene / vinyl acetate copolymer is not limited, generally known manufacturing methods such as solution polymerization, latex polymerization, and high-pressure radical polymerization are used. In particular, in order to produce an ethylene / vinyl acetate copolymer having a vinyl acetate content in the range of the component (C), it is preferably produced by solution polymerization. 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 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 to 150 ° C., preferably 55 to 70 ° C., 10 to 70 MPa (100 to 700 bar), preferably 30 to 40 MPa (300 to 400 bar). ) Under pressure. Such a production method is described in, for example, JP-A-1-101304, JP-A-7-33829, European Patent Application Publication No. A0341499, European Patent Application Publication No. A0510478, and the like. .

  The ethylene / vinyl acetate copolymer of component (C) can also be obtained as a commercial product. As a commercially available product, for example, “LEVAPREN (registered trademark)” manufactured by LANXESS, “Evaflex (registered trademark)” manufactured by Mitsui DuPont Polychemical Co., Ltd. can be selected and used. .

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

<Component (D)>
The resin composition of the present invention may preferably contain maleic anhydride-modified polyolefin as component (D). By including maleic anhydride-modified polyolefin in the resin composition, adhesion to polyvinyl chloride resin, polyolefin resin, saponified ethylene / vinyl acetate copolymer, and the like may be improved. Although the reason is not clear, it is considered that the maleic anhydride-modified polyolefin is finely dispersed in the resin composition containing the component (A), the component (B), and the component (C) as main components.

  The component (D) maleic anhydride-modified polyolefin is obtained by modifying a polyolefin resin with maleic anhydride.

  The polyolefin resin that can be used as a raw material to be modified is not limited. For example, homopolymers of α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, α-olefins or α -Olefin and other α-olefins having about 2 to 20 carbon atoms such as 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, Examples thereof include copolymers with vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, and the like.

  Specific examples of the polyolefin resin include, for example, low, medium and high density polyethylene (branched or linear) ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / vinyl alcohol copolymer (including saponified ethylene / vinyl acetate copolymer), Polyethylene resins such as ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer; propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene Polypropylene resins such as ethylene / 1-butene copolymer and propylene / 4-methyl-1-pentene copolymer; 1 Poly 1-butene resins such as butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer; and norbornene ring-opening metathesis polymers, norbornene derivatives / ethylene copolymers, etc. Examples include so-called cyclic polyolefin resins. Moreover, the chain form in the case of using a copolymer as a polyolefin resin is not limited, and any of a block copolymer, a random copolymer, a graft copolymer, and the like may be used. These polyolefin resins can be used alone or in combination of two or more.

  Among these, as polyolefin resin, a polyethylene-type resin is preferable and an ethylene-type copolymer is more preferable. In the present invention, the polyethylene resin, polypropylene resin, and poly 1-butene resin are each 50% by weight of monomer units derived from ethylene, propylene, or 1-butene in the total monomer units. The resin containing above is said.

  The method of modifying the polyolefin resin with maleic anhydride is not limited, and it can be obtained by reaction only with heat, but a radical generator may be added during the reaction. Moreover, as a method of making it react, you may use methods, such as a suspension-dispersion reaction method other than the solution modification | denaturation method and the melt modification method which do not use a solvent to make it react in a solvent. Among them, the melt modification method is preferable. As a melt modification method, a polyolefin resin, maleic anhydride, and, if necessary, a known radical generator are mixed in advance and then reacted by melting and kneading in a kneader, or a polyolefin resin melted in a kneader. Alternatively, a method of adding a mixture of maleic anhydride dissolved in a solvent or the like and a radical generator from the charging port and reacting them can be used. Usually, a Henschel mixer, a ribbon blender, a V-type blender or the like is used for mixing, and a single or twin screw extruder, a roll, a Banbury mixer, a kneader, a Brabender mixer or the like can be used for melt kneading. .

  The blending amount of maleic anhydride is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 30 parts by weight or less with respect to 100 parts by weight of the polyolefin resin. , Preferably 5 parts by weight or less, more preferably 1 part by weight or less. The blending amount of the radical generator is usually 0.001 part by weight or more, preferably 0.005 part by weight or more, more preferably 0.01 part by weight or more, and usually 3 parts by weight or less with respect to 100 parts by weight of the polyolefin resin. Preferably it is 0.5 weight part or less, More preferably, it is 0.2 weight part or less, Most preferably, it is 0.1 weight part or less.

The modification rate (graft amount) of the polyolefin resin is usually 0.01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight or more, and usually 10% by weight or less, preferably 7% by weight. % Or less, more preferably 5% by weight or less. When the resin composition of the present invention contains the component (D) having a modification rate (graft amount) within the above range, the adhesion to polyolefin resins and saponified ethylene / vinyl acetate copolymers is further improved. There is. The modification rate (graft amount) can be confirmed by a known method, and can be confirmed by ¹ H-NMR, infrared absorption spectrum, ICI emission analysis using a high-frequency plasma emission analyzer, or the like. .

  Although the melt flow rate (MFR) of a component (D) is not limited, Usually, 0.1-100 g / 10min, Preferably it is 0.5-80 g / 10min, More preferably, it is the range of 1.0-60 g / 10min. Are preferred. When the MFR is not more than the above upper limit value, the extrudability of the resulting resin composition tends to be good, and the mechanical strength in the case of a laminate tends to be improved. When the MFR is not less than the above lower limit, the fluidity is good and the moldability of the resulting resin composition tends to be improved. Here, MFR means a value at 190 ° C. and a load of 21.2 N when the polyolefin resin is a polyethylene resin or a poly 1-butene resin, and 230 ° C. when the polyolefin resin is a polypropylene resin. It means a value at a load of 21.2N.

  A commercial item can also be used as a component (D), for example, "Modic (trademark)" by Mitsubishi Chemical Corporation, "Admer (trademark)" by Mitsui Chemicals, etc. are mentioned.

  In the resin composition of the present invention, only one type of component (D) may be used, or two or more types different in polyolefin resin type, modification rate, physical properties and the like may be used in combination.

<Ingredient (E)>
The resin composition of the present invention preferably contains a fatty acid amide as the component (E). By containing a fatty acid amide in the resin composition, the moldability and handleability of a molded product obtained from the resin composition of the present invention tend to be improved. In particular, when a laminate having a layer containing the resin composition of the present invention and a layer comprising a polyvinyl chloride resin and / or a polyolefin resin is coextruded and wound into a roll, the roll sheet There is a tendency that the unwinding of the sheet from the sheet is improved. The fatty acid amide of the component (E) is not particularly limited as long as it has a structure obtained by a reaction between a fatty acid and an amine compound or ammonia. In addition, if the chemical structure is the same, it is not limited to what is obtained by the said reaction.

  The fatty acid constituting the fatty acid amide of component (E) may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Furthermore, alicyclic carboxylic acid is also included. Furthermore, the hydrocarbon group constituting the fatty acid may be substituted with a polar group, halogen or the like. Specifically, for example, saturated fatty acids are caprylic acid, lauric acid, palmitic acid, stearic acid, isostearic acid, behenic acid, behenic acid, etc., and unsaturated fatty acids are oleic acid, erucic acid, etc., alicyclic Examples of the carboxylic acid include cyclohexane carboxylic acid. Furthermore, it may be a compound having two or more carboxyl groups. By reacting these with the following amine compound, bisamide or the like can be obtained.

  The amine compound constituting the fatty acid amide of component (E) may be an aliphatic amine or an aromatic amine. The aliphatic group of the aliphatic amine may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon It may be a group. Furthermore, an alicyclic hydrocarbon group is also included. Further, the aliphatic group of the aliphatic amine or the hydrocarbon group constituting the aromatic group of the aromatic amine may be substituted with a polar group, halogen or the like. Specific examples of the aliphatic group of the aliphatic amine constituting the fatty acid amide include, for example, a capryl group, a lauryl group, a palmityl group, a stearyl group, an isostearyl group, and a beheryl group as the saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include an oleyl group and ercaryl group, and examples of the alicyclic hydrocarbon group include a cyclohexyl group. Specific examples of the aromatic group of the aromatic amine include a phenyl group, a phenylmethyl group, a toluyl group, and a xylyl group. Further, the amine compound constituting the fatty acid amide may be a compound having two or more amino groups or substituted amino groups, and can be made into bisamide or the like by reacting these with the above fatty acid.

  The amine compound constituting the fatty acid amide may be a primary amine or a secondary amine. In addition, a tertiary amine may be used at the raw material stage. By using a primary amine, an N-1 substituted aliphatic amide is obtained, and by using a secondary amine, an N, N-2 substituted fatty acid amide is obtained. Component (E) in the present invention is preferably an N, N-2 substituted fatty acid amide. Specific examples of N, N-2 substituted fatty acid amides include N-stearyl erucic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, and N-oleyl stearic acid. Examples include amides.

  In the resin composition of the present invention, the fatty acid amide of component (E) can be used alone or in combination of two or more.

<Other ingredients>
The resin composition of the present invention includes resin components other than the component (A), the component (B), the component (C) and the component (D) (hereinafter referred to as “other resins” within a range that does not significantly hinder the effects of the present invention. And additives other than the component (E), fillers and the like can be blended. Other resin may use only 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of other resins include polyolefin resins (excluding those contained in components (B) and (C)); polyphenylene ether resins; polyamide resins such as nylon 6, nylon 66, and nylon 11 Polycarbonate resin; Polyester resin such as polyethylene terephthalate and polybutylene terephthalate; (Meth) acrylic resin such as polymethyl methacrylate resin (excluding those contained in component (A)); Styrene resin such as polystyrene; etc. And other thermoplastic resins and various thermoplastic elastomers.

  In these, it is preferable to use polyolefin resin. Examples of the polyolefin resin include polyolefin resins that can be used as raw materials for the component (D).

  Various additives other than the component (E) can be blended with the resin composition of the present invention as long as the effects of the present invention are not significantly impaired. Additives other than component (E) include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, anti-aging agents, nucleating agents, plasticizers, impact modifiers, compatibilizers, antifoaming agents. Agents, thickeners, crosslinking agents, surfactants, lubricants, mold release agents, antiblocking agents, processing aids, antistatic agents, flame retardants, flame retardant aids, colorants and the like. These additives may be used alone or in combination of two or more in any combination and ratio.

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.

  Flame retardants are roughly classified into halogen-based flame retardants and non-halogen-based flame retardants, and non-halogen-based flame retardants are preferable in terms of the environment. Non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds (aluminum hydroxide and magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine and guanidine) flame retardants and inorganic compounds (borate and molybdenum) Compound) flame retardant and the like.

  The resin composition of the present invention preferably contains an antiblocking agent as an additive. By mix | blending an antiblocking agent, there exists a tendency for the blocking resistance of the pellets in the pellet manufacturing process which consists of the resin composition of this invention, subsequent storage, transport, etc. to improve. Examples of the anti-blocking agent include polyolefin fine powder, polyethylene wax and dispersions thereof.

  Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, 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, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.

<Blending amount>
In the resin composition of the present invention, the content of the component (A) with respect to the total amount of the component (A), the component (B) and the component (C) is 20 to 65% by weight. When the content of component (A) is 20% by weight or more with respect to the total amount of component (A), component (B) and component (C), adhesion to polyvinyl chloride resin and polyolefin resin in a high-temperature atmosphere On the other hand, when the content of the component (A) is 65% by weight or less, it is preferable from the viewpoint of adhesiveness with a polyolefin resin or a saponified ethylene / vinyl acetate copolymer. From these viewpoints, the content of component (A) is preferably 23% by weight or more, more preferably 25% by weight or more, while preferably 60% by weight or less, more preferably 55% by weight. It is as follows.

  In the resin composition of the present invention, the content of the component (B) with respect to the total amount of the component (A), the component (B) and the component (C) is 25 to 55% by weight. When the content of the component (B) is 25% by weight or more, it is preferable from the viewpoint of heat-resistant adhesion to a polyolefin resin, particularly a polypropylene resin. On the other hand, when the content of the component (B) is 55% by weight or less, From the viewpoints of adhesion to a vinyl chloride resin and a polyolefin resin in a high temperature atmosphere and heat resistant adhesion, it is preferable. From these viewpoints, the content of component (B) is preferably 27% by weight or more, more preferably 29% by weight or more, while preferably 50% by weight or less, more preferably 45% by weight. It is as follows.

  In the resin composition of the present invention, the content of the component (C) with respect to the total amount of the component (A), the component (B) and the component (C) is 10 to 50% by weight. When the content of the component (C) is 10% by weight or more, it is preferable from the viewpoint of heat-resistant adhesion to the polyolefin resin. On the other hand, when the content of the component (C) is 50% by weight or less, the polyvinyl chloride resin and From the viewpoint of adhesion to a polyolefin resin under a high temperature atmosphere and adhesion to a polyvinyl chloride resin, it is preferable. From these viewpoints, the content of the component (C) is preferably 13% by weight or more, more preferably 15% by weight or more, and preferably 47% by weight or less, more preferably 45% by weight. It is as follows.

  Moreover, when the resin composition of this invention contains a component (D), content of a component (D) is 0.00 with respect to a total of 100 weight part of a component (A), a component (B), and a component (C). The amount is preferably 5 to 5 parts by weight, more preferably 0.6 to 4 parts by weight, and still more preferably 0.7 to 3 parts by weight. When the content of component (D) is within the above range, adhesion to polyvinyl chloride resin and polyolefin resin is improved without impairing adhesion in high temperature atmosphere to polyvinyl chloride resin and polyolefin resin. Can be made.

  Moreover, when the resin composition of this invention contains a component (E), content of a component (E) is 0.00 with respect to a total of 100 weight part of a component (A), a component (B), and a component (C). The amount is preferably 001 to 0.5 parts by weight, more preferably 0.003 to 0.4 parts by weight, and still more preferably 0.005 to 0.3 parts by weight. When the content of the component (E) is within the above range, a laminate having a layer containing the resin composition of the present invention and a layer comprising a polyvinyl chloride resin and / or a polyolefin resin is coextruded. When rolled up, the roll sheet tends to be easily rewound.

  The content when the resin composition of the present invention contains the above-mentioned other resins is not limited, but is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight in the resin composition. . When the content of other resins exceeds the upper limit, the resulting resin composition may have insufficient adhesion to polyvinyl chloride resin, polyolefin resin, saponified ethylene / vinyl acetate copolymer, or the like.

  The content in the case where the resin composition of the present invention contains other additives other than the component (E) is not limited, but is usually 0.01 to 10% by weight in the resin composition, preferably 0.2 to 5% by weight. If the content of other additives exceeds the above upper limit, the resulting resin composition may have insufficient adhesion to polyvinyl chloride resin, polyolefin resin, saponified ethylene / vinyl acetate copolymer, etc. . In addition, when using the resin composition of this invention as a masterbatch, these additives can also be contained in the density | concentration of 2-50 times as described above, Preferably it is 3-30 times.

  The melt flow rate (MFR) of the resin composition of the present invention is not limited, but the value measured at 190 ° C. and a load of 21.2 N is usually 0.2 to 60 g / 10 min, preferably according to JIS K7210 (1999). Those having a range of 1 to 30 g / 10 min, more preferably 2 to 25 g / 10 min are suitable. If MFR is not more than the above upper limit value, the extrusion moldability of the resin composition tends to be good, and further, the mechanical strength in the case of a laminate tends to be improved. If MFR is not less than the above lower limit value, 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 the above-described components at a predetermined ratio. The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, by mixing the above-described raw material components simultaneously or in any order, a composition in which the respective components are uniformly dispersed can be obtained. For more uniform mixing and dispersion, it is preferable to melt and mix a predetermined amount 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. In addition, all raw material components and the like may be mixed while being sequentially melted, or each raw material may be appropriately blended (dry blended) and melt-mixed at the time of molding at the time of producing the desired molded article.

  The mixing method and mixing conditions are not particularly limited as long as each raw material component is uniformly mixed, but from the viewpoint of productivity, the raw materials are mixed using, for example, a tumbler blender, V blender, ribbon blender, Henschel mixer, etc. A melt kneading method using 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 preferable. The production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions. The temperature at the time of 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 it can be generally performed at 150 to 250 ° C.

[Molded body]
There is no limitation in the molded object obtained from the resin composition of this invention, It can be set as various extrusion molded objects and injection molded objects. There is also no particular limitation on the method for producing the molded body, and specifically, various molding methods such as injection molding, blow molding, extrusion molding, inflation molding, etc., and vacuum molding and compressed air using sheets obtained by these molding methods. Secondary molding methods such as molding and vacuum / pressure forming may be mentioned.
In addition, the resin composition of the present invention can be used alone to form a molded body such as a single layer sheet, but the resin composition of the present invention is excellent in adhesiveness with polyvinyl chloride resin, polyolefin resin, etc. It is more effective to use the resin composition as a laminate having one layer.

[Laminate]
The laminate using the resin composition of the present invention is a laminate laminated in two layers or three or more layers including a layer composed 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 flat shape such as a film, a sheet, and a plate shape, a pipe shape, a bag shape, and an indefinite shape. The material constituting the layer other than the resin composition layer (hereinafter sometimes referred to as other layer) is not limited, and may be not only the resin layer but also a metal layer. The material of the resin layer which comprises a laminated body is not limited, For example, what was illustrated as another resin which can be used for the resin composition of this invention is mentioned. Moreover, the resin layer which comprises a laminated body can also contain the additive which can be used for the resin composition of this invention.

  Among these, a laminate having a layer made of the resin composition of the present invention as an adhesive layer and having a polyvinyl chloride resin layer and / or a polyolefin resin layer described later is preferable. The layer structure of the laminate in this case is not limited, but is preferably a laminate in which the polyvinyl chloride resin layer and the adhesive layer and / or the adhesive layer and the polyolefin resin layer are in contact.

  When the laminate of the present invention is used for building materials such as wallpaper and decorative sheets, the resin composition of the present invention has a polyolefin resin layer that is less contaminated on the surface and that is suitable for hygiene and environment, as the outer surface side. It is preferable to use a configuration in which the adhesive layer formed is an intermediate layer and a polyvinyl chloride resin layer having good flexibility and moldability is used as the inner side. In this case, a multilayer structure in which an adhesive layer, a release layer, and the like are further provided on the polyvinyl chloride resin layer side can be used by peeling the release layer.

<Polyvinyl chloride resin layer>
The polyvinyl chloride resin layer constituting the laminate contains at least a polyvinyl chloride resin. Although the polyvinyl chloride resin which comprises a polyvinyl chloride resin layer is not limited, The homopolymer or copolymer of vinyl chloride is mentioned. The monomer copolymerizable with vinyl chloride is not limited, and examples thereof include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or an ester thereof, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, and vinylidene chloride. Alternatively, a partially crosslinked resin may be used. Further, a polymer blend of a polyvinyl chloride resin, for example, a polymer blend composed of a polyvinyl chloride resin and polyvinylidene chloride may be used. Among these, as the polyvinyl chloride resin used for the polyvinyl chloride resin layer, a homopolymer of vinyl chloride is preferable.

  Although the average degree of polymerization of the polyvinyl chloride resin used for the polyvinyl chloride resin layer is not limited, it is usually 500 to 6000, preferably 800 to 3000. Further, the reduced viscosity (K value) of the polyvinyl chloride resin is not limited, but it is usually 50 to 110, preferably 60 to 90, as a value based on JIS K7367-2.

  The manufacturing method of a polyvinyl chloride resin is not limited, For example, it can manufacture by suspension polymerization method, block polymerization method, emulsion polymerization method, etc. Alternatively, plastisol or aqueous latex in which polyvinyl chloride resin fine particles are dispersed in an organic medium may be used.

The polyvinyl chloride resin used for the polyvinyl chloride resin layer preferably contains a plasticizer.
Although the plasticizer used for the polyvinyl chloride resin is not limited, specifically, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, Phthalic acid esters having an alkyl group having 1 to 12 carbon atoms such as butylbenzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisocumyl phthalate, dinonyl phthalate; Diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dihex Ruazelate, diisooctyl azelate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, methylacetyl Fatty acid esters such as ricinolate and butylacetylricinolate; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, tetra- (2-ethylhexyl) pyromellitate, tetra-n-octyl・ Pyromellitate, Tetraisooctyl ・ Pyromellitate, Biphenyltetracarboxylic acid tetrabutyl ester, Biphenyltetracarboxylic acid tetrapentyl ester, Bife Aromatic carboxylic acid esters such as tetratetracarboxylic acid tetrahexyl ester; tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate , Orthophosphoric acid esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate; chlorinated paraffin; chlorinated fatty acid ester; epoxidized soybean oil; epoxidized linseed oil; epoxy butyl stearate, epoxy octyl stearate; Examples include methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. These plasticizers may be used alone or in combination of two or more compounds.

  Although the compounding quantity in the case of using a plasticizer is not limited, It is 1-150 weight part normally with respect to 100 weight part of polyvinyl chloride resin, Preferably it is 15-120 weight part, More preferably, it is 20-100 weight part. It exists in the tendency for the softness | flexibility of the laminated body of this invention to become it favorable that the compounding quantity of a plasticizer is more than the said lower limit. On the other hand, when the blending amount of the plasticizer is not more than the above upper limit value, bleeding out of the plasticizer from the laminate of the present invention is suppressed, and the moldability is also improved.

  The polyvinyl chloride resin used for the polyvinyl chloride resin layer may contain a stabilizer. The stabilizer used in the polyvinyl chloride resin is not limited, but can be appropriately selected from known stabilizers for polyvinyl chloride resin, for example, 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 Examples thereof include stabilizers mainly composed of inorganic salts such as magnesium, aluminum and silicon such as sites. These stabilizers may use only 1 type of compound, or may use 2 or more types of compounds together.

  Although the compounding quantity in the case of using a stabilizer is not limited, It is 1-30 weight part normally with respect to 100 weight part of polyvinyl chloride resin, Preferably it is 2-20 weight part, More preferably, it is 3-15 weight part. When the stabilizer is blended in the above range, the thermal stability and moldability tend to be good.

<Polyolefin resin layer>
The polyolefin resin layer constituting the laminate contains at least a polyolefin resin. The polyolefin resin that can be used for the polyolefin resin layer is not limited, and examples thereof include resins exemplified as the polyolefin resin before the modification of the component (D). An ethylene / vinyl acetate copolymer can also be used. These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.

The polyolefin resin suitable for the polyolefin resin layer varies depending on the use and required characteristics of the laminate of the present invention, but when used for building materials, a polyethylene resin or a polypropylene resin is suitable. The polyethylene resin is more preferably a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and the polypropylene resin is a copolymer of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms. Is more preferable.
In particular, the polyolefin resin layer is preferably a propylene-based resin layer because the resin composition of the present invention has particularly good adhesion to the polypropylene-based resin by including the above-described component (B).

  The melt flow rate (MFR) of the polyolefin resin used for the polyolefin resin layer is not limited, but is usually 0.1 to 100 g / 10 minutes, preferably 0.5 to 80 g / 10 minutes, more preferably 1.0 to 60 g / A range of 10 minutes is preferred. When the MFR is within the above range, the moldability of the laminate tends to be good. Here, MFR means a value at 190 ° C. and a load of 21.2 N when the polyolefin resin is a polyethylene resin or a poly 1-butene resin, and 230 when the polyolefin resin is a polypropylene resin. It means the value at ° C and load 21.2N.

<Method for producing laminate>
The method for producing the laminate of the present invention is not limited, and various conventionally known methods can be employed. In particular, since the resin composition of the present invention has good adhesion, a laminate having good adhesion can be obtained by the following molding method without performing dry lamination using an organic solvent. . Specifically, for example, an inflation film, a T-die film, a sheet, a pipe, and the like are supplied by a co-extrusion method in which individual molten resins melted by an extruder are supplied to a multilayer die and laminated in the die. And co-injection molding in which molten individual resins are injected into the same mold with a time lag. Moreover, the extrusion lamination molding which shape | molds the resin film which comprises any one layer of each layer previously, and melt-extrudes another layer to this can also be employ | adopted. Furthermore, it is also possible to form a laminate by previously forming a resin film that constitutes each layer, and applying heat to these layers and fusing them.

  Moreover, the laminated body of this invention can also be made into an extending | stretching laminated body by extending | stretching this, after obtaining a laminated body by the above forming methods. The stretched laminate may be heat-set, or may be a product without being heat-set. When heat setting is not performed, it can be used as a shrink film because it has the property of releasing the stress and then shrinking by heating the stretched laminate. Furthermore, these can be made into a draw-formed container or the like through secondary processing such as vacuum forming or 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 configuration, application, final product shape, required physical properties, etc., but is usually 30 to 500 μm, It is preferable that it is 40-400 micrometers, and it is especially preferable that it is 50-300 micrometers. In the examples described later, the laminate is thicker than the above upper limit in order to evaluate 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. If the thickness of the resin composition layer is equal to or greater than the lower limit, the adhesiveness is good, and if it is equal to or less than the upper limit, the film strength tends to be improved.

[Usage]
Since the resin composition of the present invention has good adhesion to polyvinyl chloride resin, polyolefin resin, saponified ethylene / vinyl acetate copolymer, etc., the resulting laminate is a building material such as wallpaper or decorative sheet. In addition, it can be suitably used as protective films, antifouling films, packaging materials and the like for various molded products. Among these, it can be suitably used as wallpaper in particular. When using the laminated body of this invention as wallpaper, you may provide an adhesion layer, a base material layer, an antifouling layer, a mold release layer, etc. further. Further, physical treatment such as embossing may be performed, and in this case as well, good interlayer adhesion can be maintained. Furthermore, the resin composition and laminate of the present invention can be suitably used for automobile interior materials.

  EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

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

<Component (A)>
(A-1)
“Clarity (registered trademark) LA4285” manufactured by Kuraray Co., Ltd., an acrylic thermoplastic elastomer (hard segment: polymer block of methyl methacrylate (50 wt%), soft segment: polymer block of n-butyl acrylate (50 wt%) ), Weight average molecular weight (Mw): 58,000, molecular weight distribution (Mw / Mn): 1.13, glass transition temperature (Tg): 141 ° C., 29 ° C., MFR: 1.5 g / 10 min (190 ° C., 21.2N) (ISO 1133)), specific gravity: 1.11 (ISO 1183), duro A hardness: 46 (ISO 7619))

<Component (B)>
(B-1)
Propylene-based elastomer “Tafmer (registered trademark) PN-2070” (density (ASTM D1505): 867 kg / m ³ , MFR: 7.0 g / 10 min (230 ° C., 21.2 N)) (JIS K7210 ( 1990), melting point 140 ° C.)

<Ingredient (C)>
(C-1)
“Evaflex (registered trademark) V523” manufactured by Mitsui DuPont Polychemical Co., Ltd. (vinyl acetate content: 33 wt%, MFR: 14 g / 10 min (190 ° C., 21.2 N)) (JIS K7210 (1990), density: 0.960 g / cm ³ , melting point: 63 ° C.)
(C-2)
“Evaflex (registered trademark) EV170” manufactured by Mitsui DuPont Polychemical Co., Ltd. (vinyl acetate content: 33 wt%, MFR: 1 g / 10 min (190 ° C., 21.2 N) (JIS) K7210 (1990), density: 0.960 g / cm ³ , melting point: 62 ° C.)
(C-3)
“Evaflex (registered trademark) V5274” manufactured by Mitsui DuPont Polychemical Co., Ltd. (vinyl acetate content: 17% by weight, MFR: 0.8 g / 10 minutes (190 ° C., 21.2 N)) (JIS K7210 (1990), density: 0.940 g / cm ³ , melting point: 89 ° C.)

<Component (D)>
(D-1)
Maleic anhydride-modified polyethylene obtained by melt-kneading a linear low density polyethylene polymerized with a metallocene-based catalyst, maleic anhydride and an organic peroxide in an extruder (modification rate: 0.59% by weight, MFR: 8.8 g / 10 min (190 ° C., 21.2 N)

[Examples 1 to 4 and Comparative Examples 1 to 4]
<Preparation of sample for evaluation>
Each raw material component is used in the blending ratio shown in Table 1, and is kneaded at 180 to 200 ° C. using an ultra-small kneader and a molding machine, and a 1 mm thick rigid polyvinyl chloride resin sheet (Sumicon VM (Mitsubishi Chemical Corporation) (Registered trademark) “3615G” obtained by compression molding at 190 ° C.), 300 μm thick polypropylene resin film (Novatech (registered trademark) “FY6” manufactured by Nippon Polypropylene Co., Ltd.) obtained by film molding at 240 ° C. Are placed in a mold and insert injection is performed, so that a rigid polyvinyl chloride resin sheet and a polypropylene resin film are integrated with an adhesive layer of each resin composition having a thickness of 3 mm and 3.9 mm, respectively. A laminated sheet evaluation sample 1 (10 mm × 800 mm) was produced.

[Evaluation method]
<Adhesive strength>
The samples for evaluation of Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to a T peel peel test at a speed of 100 mm / min at each temperature of 23 ° C., 60 ° C., and 80 ° C. in accordance with JIS K6854. .
The peel strength of the T peel peel test is shown in Table 1 as the adhesive strength.
Of the evaluation results in the table, “vs. PVC” and “vs. PP” mean the adhesive strength between the hard polyvinyl chloride resin sheet, the polypropylene resin film and the resin composition layer (adhesive layer), respectively.

  From Table 1, what uses the resin composition of this invention containing a component (A), a component (B), and a component (C) is adhesion with a polyvinyl chloride resin also in a high temperature atmosphere of 60 degreeC or more. It can be seen that the strength is good.

On the other hand, the resin composition containing only component (A) and not component (B), which is a component responsible for adhesion to polypropylene resin, and component (C), which is a component contributing to adhesion to polyvinyl chloride resin. In Comparative Example 1 using the product, good adhesive strength was not exhibited in both the polyvinyl chloride resin and the polypropylene resin in an atmosphere at 23 ° C.
Further, a resin containing only component (A) and component (B), but not containing component (C), Comparative Example 2 and components (A) to (C), but containing a small amount of component (B). In Comparative Example 4 using the composition, good adhesive strength with the polypropylene resin was not expressed. Furthermore, in Comparative Example 3 using a resin composition containing component (A) to component (C) but having a large amount of component (B), good adhesive strength with the polyvinyl chloride resin was developed. There wasn't.

Claims (9)

Including the following component (A), component (B) and component (C), component (A) is 20 to 65% by weight, component (B) is 25 to 55% by weight, and component (C) ) In an amount of 10 to 50% by weight.
Component (A): Acrylic thermoplastic elastomer component (B): Propylene elastomer component (C): Density (ASTM D1505) of 855 to 895 kg / m ³ : Ethylene / vinyl acetate copolymer   The resin composition according to claim 1, wherein the component (A) has a hard segment composed of a polymer of methyl methacrylate and a soft segment composed of a polymer of n-butyl acrylate. The following component (D) is included, and the content thereof is 0.5 to 5 parts by weight with respect to 100 parts by weight in total of the component (A), the component (B), and the component (C). The resin composition described in 1.
Component (D): Maleic anhydride modified polyolefin   The molded object formed by shape | molding the resin composition of any one of Claims 1 thru | or 3.   The laminated body which has a layer containing the resin composition of any one of Claims 1 thru | or 3, and another layer.   The laminated body which has a polyvinyl chloride resin layer, the contact bonding layer containing the resin composition of any one of Claims 1 thru | or 3, and the polyolefin resin layer.   The laminate according to claim 6, wherein the polyvinyl chloride resin layer and the adhesive layer and / or the adhesive layer and the polyolefin resin layer are in contact with each other.   The laminate according to claim 6 or 7, wherein the polyolefin resin layer is a polypropylene resin layer.   The building material which contains the laminated body of any one of Claims 6 thru | or 8 as a structure.