TWI691544B - Resin composition, molded article and laminate - Google Patents

Abstract

Provided is a resin composition, etc., in which a methacrylic resin and a lubricant contains a resin composition that hardly generates gel during melt molding.

The resin composition of the present invention contains a resin mixture (M) and a lubricant, and the resin mixture (M) contains a methacrylic resin (A), an ethylene containing a structural unit of formula (1) and a structural unit of formula (2) Copolymer (B). The lubricant satisfies the conditions of (i) and (ii) with respect to 100 parts by mass of the resin mixture (M).

(i) Lubricants that do not contain monoglyceride esters containing saturated fatty acids having 10 to 24 carbon atoms (x1), or lubricants containing 0.1 mass parts or less of monoglyceride esters containing saturated fatty acids having 10 to 24 carbon atoms (x1); (ii) will contain 1 selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides and fatty acid esters (wherein the lubricant (x1), and the lubricant (x1) At least one lubricant (Y) in the group of lubricants (except for lubricants (x2) of fatty acid esters having two or more hydroxyl groups in the molecule) is set to 0.001 to 2 parts by mass.

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group.)

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group.)

Description

Resin composition, molded product and laminate

The present invention relates to a resin composition containing methacrylic resin, ethylene copolymer and lubricant. In addition, it relates to a molded product and a laminate including the resin composition.

The methacrylic resin excellent in transparency, scratch resistance, weather resistance, etc. may contain a lubricant for the purpose of improving mold releasability and processability (for example, Patent Documents 1 and 2). However, by containing a lubricant, the physical properties are improved, but on the other hand, the heat resistance or moisture resistance decreases. The decrease in heat resistance causes a dimensional change of the molded body using the methacrylic resin composition, so it becomes a problem in applications requiring dimensional accuracy. In addition, the decrease in moisture resistance is also a problem for the same reason.

As a resin having high heat resistance and moisture resistance, a copolymer resin containing styrene and maleic anhydride is known. For example, Non-Patent Document 1 reports that a copolymer resin containing 18 to 35% by mass of maleic anhydride containing styrene and maleic anhydride has higher heat resistance than methacrylic resin. In addition, Non-Patent Document 2 describes that the copolymerized resin of styrene and maleic anhydride will become a low water absorption resin, and Patent Documents 3 and 4 disclose that The copolymer resin of styrene and maleic anhydride is blended with the composition of methacrylic resin.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-180454

[Patent Document 2] Japanese Patent No. 3400104

[Patent Document 3] International Publication No. 2014/021264

[Patent Document 4] Japanese Unexamined Patent Publication No. 2014-160583

[Non-patent literature]

[Non-Patent Document 1] XIRAN(R)SMA "New tricks in polymer blends" [POLYSCOPE] (http://www.bpri.org/documenten/2008_8_flippo.pdf)

[Non-Patent Document 2] THOMASNET NEWS “Polyscope Polymers Expands Scope of XIRAN(R)SMA as Additive for Amorphous Thermoplastics” [2010, POLYSCOPE Corporation] (http://news.thomasnet.com/companystory/Polyscope-Polymers-Expands -Scope-of-XIRAN-SMA-as-Additive-for-Amorphous-Thermoplastics-573050)

However, when the resin composition having improved heat resistance and moisture resistance contains a lubricant and is melt-molded under high-temperature conditions, a droplet-like foreign substance quantified by crosslinking and a polymer is quantified, that is, a gel is formed. Of situation. This gel sometimes has a problem of foreign matter defects that become a molded product, and may also damage the appearance of the product.

In addition, in a specific application requiring a high-quality appearance, it is filtered by a filter during melt molding, but there is also a problem that the filtration promotes gelation. That is, the filter has the effect of capturing and crushing the gel in the resin composition that was contaminated during the polymerization process or the gel that occurred before the filter in the melt molding process, but on the other hand, there will be a long-term resin It stays in the filter and contributes to the gelation problem.

The present invention has been accomplished in view of the above-mentioned problems, and its object is to provide a resin composition, a molded product, and a laminate that do not easily generate gel during melt molding in a resin composition containing a methacrylic resin and a lubricant .

As a result of repeated and intensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved in the following aspects, and completed the present invention.

[1] A resin composition containing a resin mixture (M) and a lubricant, the resin mixture (M) containing 5 to 90% by mass of methacrylic resin (A), and at least 10 to 95% by mass The ethylene-based copolymer (B) composed of the structural unit of the aromatic vinyl compound (b1) represented by the following general formula (1) and the structural unit derived from the cyclic acid anhydride (b2) represented by the following general formula (2) ), and the lubricant satisfies the following conditions (i) and (ii).

(i) Lubricant (x1) that does not contain monoglycerides containing saturated fatty acids having 10 to 24 carbon atoms, or contains 0.1 or less parts by mass of carbon atoms relative to 100 parts by mass of the resin mixture (M) 10~24 saturation Lubricant (x1) of fatty acid monoglyceride; (ii) 0.001 to 2 parts by mass of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, fats, based on 100 parts by mass of the resin mixture (M) Group of amides and fatty acid esters (excluding lubricant (x1) and lubricants (x2) other than the lubricant (x1) containing fatty acid esters having two or more hydroxyl groups in one molecule) Lubricant (Y) of at least one of them.

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group.)

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group.)

[2] The resin composition of [1], wherein the lubricant (Y) is at least one selected from the group consisting of an aliphatic monohydric alcohol having 12 to 18 carbon atoms and a saturated fatty acid having 16 to 24 carbon atoms By.

[3] The resin composition according to [1] or [2], wherein the resin mixture (M) contains 30 to 60% by mass of methacrylic resin (A) and 40 to 70% by mass of ethylene-based copolymer (B ).

[4] The resin composition according to any one of [1] to [3], wherein the ethylene-based copolymer (B) contains 50 to 84% by mass of the structural unit derived from the aromatic vinyl compound (b1) and contains 15 ~49% by mass of structural units derived from cyclic anhydride (b2), and 1 to 35% by mass of structural units derived from methacrylate (b3).

[5] The resin composition of [4], wherein the methacrylate (b3) is methyl methacrylate.

[6] The resin composition according to any one of [1] to [5], wherein the glass transition temperature is 115 to 160°C.

[7] The resin composition according to any one of [1] to [6], wherein the saturated water absorption in water at 23° C. is 0.3 to 1.9% by mass.

[8] The resin composition according to any one of [1] to [7], wherein the lubricant further satisfies the following conditions (iii) and (iv).

(iii) Lubricant (x2) which does not contain lubricant (x2), or which is 0.1 parts by mass or less relative to 100 parts by mass of resin mixture (M); (iv) Lubricant (x1) and lubricant (x2) The total of is in the range of 0 to 0.1 with respect to 100 parts by mass of the resin mixture (M).

[9] The resin composition according to any one of [1] to [8], wherein the total amount of the lubricant is 0.1 part by mass or more relative to 100 parts by mass of the resin mixture (M).

[10] A molded article comprising the resin composition of any one of [1] to [9].

[11] A laminate comprising a layer composed of the resin composition (C1) according to any one of [1] to [9], and a thermoplastic resin composition having a glass transition temperature in the range of 130 to 160°C (T) Consists of layers.

[12] The laminate according to [11], wherein the thermoplastic resin composition (T) is a polycarbonate-containing resin composition.

[13] The laminate according to [11] or [12], wherein the difference in glass transition temperature between the thermoplastic resin composition (T) and the aforementioned resin composition is 30° C. or less.

[14] The laminate according to any one of [11] to [13], which further has a scratch-resistant layer as claimed in at least one surface.

The resin composition of the present invention is shown to provide a resin composition which does not easily form a gel during melt molding in a resin composition containing a methacrylic resin, an aromatic vinyl-cyclic anhydride copolymer and a lubricant , Excellent effects of molded products and laminates.

[Forms for carrying out the invention]

Hereinafter, an example of an embodiment applied to the present invention will be described. In addition, the numerical value specified in this specification represents the value obtained when measured by the method described in the below-mentioned Example. For example, the weight-average molecular weight Mw and the number-average molecular weight Mn are the standard polystyrene conversion values measured by GPC (gel permeation chromatography), and represent the values obtained when measured by the method described in Examples described later. In addition, the numerical value "A~B" specified in this specification means a range that satisfies the numerical value A and the value greater than the numerical value A, and the numerical value B and the value less than the numerical value B.

[Resin composition]

The resin composition of the present invention contains 100 masses of resin mixture (M) Parts, and a specific lubricant, the resin mixture (M) contains a methacrylic resin (A), and a structural unit containing an aromatic vinyl compound (b1) represented by the following general formula (1) And an ethylene-based copolymer (B) derived from the structural unit of the cyclic acid anhydride (b2) represented by the following general formula (2) (hereinafter, referred to as "SMA resin (B)").

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group.)

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group.)

[Resin mixture (M)]

The resin mixture (M) of the present invention contains methacrylic resin (A) and SMA resin (B).

The content of the methacrylic resin (A) in the resin mixture (M) is in the range of 5 to 90% by mass. The content of the methacrylic resin (A) in the resin mixture (M) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and most preferably 30% by mass or more. Moreover, the content of the methacrylic resin (A) in the resin mixture (M) is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75 Below mass%, the best is below 60 mass%. The layer containing the resin composition of the present invention is made excellent in scratch resistance by setting the content of the methacrylic resin (A) in the resin mixture (M) to 5% by mass or more, by 90% by mass In the following, when laminated with other layers, the occurrence of warpage under high temperature and high humidity can be suppressed.

The methacrylic resin (A) is a resin containing structural units derived from methacrylate. Examples of the methacrylate include methyl methacrylate (hereinafter referred to as "MMA"), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-methacrylate Butyl ester, isobutyl methacrylate, tertiary butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate Alkyl methacrylates such as esters, decyl methacrylate, dodecyl methacrylate, etc.; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, methylmethacrylate Cycloalkyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl methacrylate, etc. cycloalkyl methacrylate; phenyl methacrylate aryl methacrylate; Aralkyl methacrylates such as benzyl acrylate; etc., from the viewpoint of availability, preferably MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methyl alcohol The n-butyl acrylate, isobutyl methacrylate, and tertiary butyl methacrylate are preferably MMA. The content of the structural unit derived from methacrylate in the methacrylic resin (A) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and may be derived only from the methyl group The structural unit of acrylate.

Also, from the viewpoint of heat resistance, methacrylic resin (A) It is preferably 90% by mass or more of the structural unit derived from MMA, more preferably 95% by mass or more, still more preferably 98% by mass or more, and it may be a structural unit derived from MMA only.

In addition, the methacrylic resin (A) may contain structural units derived from monomers other than methacrylate. For this other monomer, methyl acrylate (hereinafter referred to as "MA"), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate , Hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxy acrylate Butyl ester, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate Acrylates such as esters, allyl acrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, isocampreyl acrylate, 3-dimethylaminoethyl acrylate, etc. Preferred are acrylates of MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, etc., more preferred are MA and ethyl acrylate, and the most preferred are MA. The content of structural units derived from these other monomers in the methacrylic resin (A) is preferably 10% by mass or less in total, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The methacrylic resin (A) is obtained by the above-mentioned methacrylate alone or by polymerizing methacrylate and other monomers of arbitrary components. In the case of using a plurality of monomers in the polymerization, the monomer mixture is usually prepared by mixing the plurality of monomers, and then supplied for polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferable to perform radical polymerization by methods such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method.

The weight average molecular weight of the methacrylic resin (A) (hereinafter, referred to as "Mw") is preferably 40,000 to 500,000. When the Mw is 40,000 or more, the laminate of the present invention becomes excellent in scratch resistance and heat resistance, and when it is 500,000 or less, the resin mixture (M)-based molding processability is excellent, and the laminate of the present invention is improved Productivity.

The content of SMA resin (B) in the resin mixture (M) is in the range of 10 to 95% by mass. The content of the SMA resin (B) in the resin mixture (M) is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and most preferably 40% by mass or more. The content of the SMA resin (B) in the resin mixture (M) is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and most preferably 70% by mass or less. The layer composed of the resin composition of the present invention, by setting the content of the SMA resin (B) in the resin mixture (M) to 10% by mass or more, when laminated with other layers, can be suppressed under high temperature and high humidity The occurrence of warpage; if it is 95% by mass or less, the scratch resistance is excellent.

The SMA resin (B) is an ethylene-based copolymer (B) containing at least a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a cyclic anhydride.

The alkyl groups independently represented by R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) are preferably methyl, ethyl, n-propyl and isopropyl Group, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl Alkyl, decyl, dodecyl and other alkyl groups with a carbon number of 12 or less, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary C4 or lower alkyl groups such as butyl.

As for R ¹ , hydrogen atom, methyl group, ethyl group and tertiary butyl group are preferred. R ² , R ³ and R ⁴ are preferably a hydrogen atom, a methyl group and an ethyl group.

The content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. In addition, the content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 84% by mass or less, more preferably 82% by mass or less, and still more preferably 80% by mass or less. When the content is in the range of 50 to 84% by mass, the resin mixture (M) becomes excellent in moisture resistance and transparency. However, when the SMA resin (B) contains two monomers of the aromatic vinyl compound (b1) and the cyclic anhydride (b2), the structure derived from the aromatic vinyl compound (b1) in the SMA resin (B) The content of the unit is preferably in the range of 50 to 85% by mass.

Examples of the aromatic vinyl compound (b1) include styrene; 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tertiary Each alkyl-substituted styrene such as butylstyrene; α-alkylstyrene such as α-methylstyrene and 4-methyl-α-methylstyrene are preferred from the viewpoint of availability It is styrene. These aromatic vinyl compounds (b1) may be used alone or in combination.

The content of the structural unit derived from the cyclic anhydride (b2) in the SMA resin (B) is preferably 15% by mass or more, and more preferably 18% by mass or more , It is further preferably 20% by mass or more. In addition, the content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 49% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. By setting the content in the range of 15 to 49% by mass, the resin mixture (M) becomes excellent in heat resistance and transparency. However, when the SMA resin (B) contains two monomers of the aromatic vinyl compound (b1) and the cyclic anhydride (b2), the structural unit derived from the cyclic anhydride (b2) in the SMA resin (B) The content is preferably in the range of 15 to 50% by mass.

Examples of the cyclic acid anhydride (b2) include maleic anhydride, citraconic anhydride, and dimethylmaleic anhydride. From the viewpoint of availability, maleic anhydride is preferred. The cyclic acid anhydride (b2) may be used alone or in combination.

The SMA resin (B) preferably contains a structural unit derived from methacrylate in addition to the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). The content of the structural unit derived from methacrylate (b3) in the SMA resin (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. In addition, the content of the structural unit derived from methacrylate (b3) in the SMA resin (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 26% by mass or less. By setting the content in the range of 1 to 35% by mass, it is possible to further achieve excellent transparency and thermal stability.

Examples of the methacrylate (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methyl methacrylate. base Tertiary butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate, etc. Among these methacrylates, alkyl methacrylates having an alkyl group of 1 to 7 carbon atoms are preferred; from the viewpoint of excellent heat resistance and transparency of the obtained SMA resin, MMA is particularly preferred. Moreover, methacrylate may be used individually by 1 type, and may use multiple types together.

The SMA resin (B) may have structural units derived from monomers other than the aromatic vinyl compound (b1), cyclic anhydride (b2), and methacrylate (b3). For this other monomer, it can be listed as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, hexyl acrylate, acrylic acid 2- Ethylhexyl ester, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, acrylic acid Acrylic esters such as phenyl ester, tolyl acrylate, benzyl acrylate, isobornyl acrylate, 3-dimethylaminoethyl acrylate. These other monomers may be used alone or in combination. In the SMA resin (B), the content of the structural unit derived from the other monomer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The SMA resin (B) is obtained by polymerizing at least the monomers of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2). As a monomer, it can be polymerized by adding methacrylate (b3) and other monomers with arbitrary components . In this polymerization, the monomer mixture is usually mixed to prepare a monomer mixture, and then supplied for polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferable to perform radical polymerization by a method such as a bulk polymerization method or a solution polymerization method.

The Mw of the SMA resin (B) is preferably in the range of 40,000 to 300,000. By setting the Mw to 40,000 or more, the laminate system of the present invention is excellent in scratch resistance and impact resistance, and when it is 300,000 or less, the resin mixture (M) system is excellent in moldability and the resin composition of the present invention is improved Productivity of formed products.

The mass ratio of methacrylic resin (A) to SMA resin (B) contained in the resin mixture (M) (methacrylic resin (A)/SMA resin (B)) prevents warping at high temperature and high humidity The viewpoints of occurrence, transparency, and scratch resistance are preferably in the range of 5/95 to 90/10. The mass ratio is more preferably 10/90 or more, further preferably 15/85 or more, and particularly preferably 20/80 or more. In addition, the mass ratio is more preferably 85/15 or less, further preferably 80/20 or less, and particularly preferably 75/25 or less.

As the mixing system of the methacrylic resin (A) and the SMA resin (B), for example, a melt mixing method, a solution mixing method, and the like can be used. The melt-mixing method system uses, for example, a single-axis or multi-axis kneading machine, an open roll mill, a Banbury sealed kneader, a kneader, etc., as required, in nitrogen, argon, helium, etc. Melt mixing in an inert gas environment. In the solution mixing method, methacrylic resin (A) and SMA resin (B) are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone.

The resin mixture (M) is within the range that does not impair the effects of the present invention, and may contain other than methacrylic resin (A) and SMA resin (B) Other polymers. Examples of the other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorcamene, and ethylidene ion polymers; Styrene-based resins such as polystyrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc.; methyl methacrylate- Styrene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomer; polyphenylene sulfide , Polyetheretherketone, polyester, polystyrene, polyphenylene ether, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol Thermoplastic resins such as copolymers and polyacetals; thermosetting resins such as phenolic resins, melamine resins, polysiloxane resins, and epoxy resins; polyvinylidene fluoride, polyurethanes, and modified polyphenylene ethers , Polyphenylene sulfide, polysiloxane modified resin; acrylic rubber, polysiloxane rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, SIS; olefin-based rubbers such as IR, EPR, EPDM, etc. Other polymers may be used alone or in combination.

The content of the other polymer in the resin mixture (M) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The resin mixture (M) may contain various additives as needed. Examples of the additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes/pigments, Light diffusing agent, matting agent, impact modifier, phosphor, etc. The content of these additives can be appropriately set within the range that does not impair the effects of the present invention, relative to 100 parts by mass of the resin mixture (M), preferably, for example, the content of the antioxidant is 0.01 to 1 part by mass, the content of the ultraviolet absorber is 0.01 to 3 parts by mass, and the content of the light stabilizer is 0.01 to 3 parts by mass The content of the lubricant is 0.01 to 3 parts by mass, and the content of the dye/pigment is 0.01 to 3 parts by mass.

When the resin mixture (M) contains other polymers and/or additives, it can be added when the methacrylic resin (A) and/or SMA resin (B) is polymerized, and the methacrylic resin (A) and SMA resin can be mixed It is added at the time of (B), and you may add after mixing methacrylic resin (A) and SMA resin (B).

The glass transition temperature of the resin mixture (M) is preferably in the range of 120 to 160°C. The lower limit of the glass transition temperature is more preferably 130°C or higher, and still more preferably 140°C or higher. In addition, the upper limit of the glass transition temperature is more preferably 155°C or lower, and still more preferably 150°C or lower. By setting the glass transition temperature to be in the range of 120 to 160°C, it is possible to suppress the occurrence of warpage of the molded body composed of the resin composition of the present invention under high temperature and high humidity. In addition, the glass transition temperature in this specification refers to the temperature at the time of a temperature rise rate of 10 degreeC/min measured using a differential scanning calorimeter, and calculated by the midpoint method.

The melt flow rate of the resin mixture (M) (hereinafter, referred to as "MFR") is preferably in the range of 1 to 10 g/10 minutes. The lower limit of the MFR is more preferably 1.5 g/10 minutes or more, and still more preferably 2.0 g/10 minutes. In addition, the upper limit of the MFR is more preferably 7.0 g/10 minutes or less, and still more preferably 4.0 g/10 minutes or less. When the MFR is in the range of 1 to 10 g/10 minutes, the stability of heat-melting molding is good. In addition, in this manual The MFR of the resin mixture (M) refers to a value measured using a melt indexer at a temperature of 230°C and a load of 3.8 kg.

[Lubricant]

Lubricants are well-known additives added to resins in order to impart anti-friction properties and mold release properties. As lubricants, higher alcohol-based lubricants, hydrocarbon-based lubricants, fatty acid-based lubricants, fatty acid metal salt-based lubricants, aliphatic amide-based lubricants, ester-based lubricants, and the like are known. Among these, the lubricant used in the present invention satisfies the following conditions (i) and (ii).

(i) Lubricant (x1) that does not contain monoglycerides containing saturated fatty acids having 10 to 24 carbon atoms, or contains 0.1 or less parts by mass of carbon atoms relative to 100 parts by mass of the resin mixture (M) Lubricant for monoglycerides of saturated fatty acids 10 to 24 (x1).

(ii) For 100 parts by mass of the resin mixture (M), it will be selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides and fatty acid esters (however, the lubricant (x1) and the lubricant The lubricant (Y) of at least one member of the group other than the agent (x1) that contains a fatty acid ester having two or more hydroxyl groups in one molecule (except the lubricant (x2)) is set to 0.001 to 2 parts by mass.

From the viewpoint of the balance between the heat resistance of the resin composition and the appearance quality of the molded body, the total amount of the lubricant is preferably in the range of 0.001 to 3 parts by mass relative to 100 parts by mass of the resin mixture (M). By setting in this range, the heat resistance of the resin composition will not be significantly reduced, the internal slip of the resin composition will be improved, and the metal attached to the drum, propeller, roll, etc. will be prevented from condensing during melt molding such as extrusion molding On the surface, a molded body excellent in appearance quality is obtained. The total amount of lubricant is more preferably 0.005 parts by mass or more, and still more preferably 0.01 parts by mass or more. The step is more preferably 0.1 parts by mass or more, and most preferably 0.15 parts by mass or more. The total amount of lubricant is more preferably 2 parts by mass or less, and still more preferably 1 part by mass or less.

Lubricant (x1) is a lubricant containing monoglycerides of saturated fatty acids having 10 to 24 carbon atoms, and lubricant (x2) is a fatty acid having two or more hydroxyl groups in one molecule in addition to the aforementioned lubricant (x1) Ester lubricant. That is, when the lubricant (X) is regarded as a lubricant containing a fatty acid ester having two or more hydroxyl groups in one molecule, the lubricant (X) includes a lubricant (x1) and a lubricant (x2), The lubricant (x2) is the lubricant (x1) removed from the lubricant (X).

The lubricant (Y) is at least at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (except for lubricants (x1) and lubricants (x2)) One. That is, the lubricant (Y) is removed from the higher alcohol, hydrocarbon, fatty acid, fatty acid metal salt, aliphatic amide, and fatty acid ester.

Examples of the lubricant (x1) include monoglycerides such as glycerol monostearate and glycerol monobehenate. Lubricant (x1) can be used alone or in combination. In addition, glycerol monostearate and stearic acid monoglyceride are terms indicating the same compound.

The amount of lubricant (x1) is 0 to 0.1 parts by mass with respect to 100 parts by mass of the resin mixture (M). The amount of the lubricant (x1) relative to 100 parts by mass of the resin mixture (M) is preferably 0.05 parts by mass or less, more preferably 0.03 parts by mass or less, and still more preferably 0.01 parts by mass or less. When the amount of lubricant (x1) is too large, it may react with the cyclic anhydride (b2) unit of the ethylene-based copolymer (B) to form a gel when the resin composition is melt-molded. In addition, the molded article tends to cause foreign matter defects or poor appearance.

Examples of the lubricant (x2) include partial esters of polyol fatty acids other than the lubricant (x1), and specific examples include neopentyl tetrastearate and stearic acid. Sorbitan mono/diester, etc. such as neopentaerythritol mono/diester, sorbitan monostearate, sorbitan monopalmitate, etc.

The lubricant (x2) has a fatty acid carbon number of preferably 10 to 40, more preferably 10 to 24, and still more preferably 14 to 24. In addition, the fatty acid may be an unsaturated fatty acid or a saturated fatty acid. Lubricant (x2) can be used alone or in combination.

The lubricant (Y) is at least at least one selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (except for lubricants (x1) and lubricants (x2)) One. The lubricant (Y) is preferably at least one selected from the group consisting of an aliphatic monohydric alcohol having 12 to 18 carbon atoms and a saturated fatty acid having 16 to 24 carbon atoms, and more preferably 12 to 12 carbon atoms 18 aliphatic monohydric alcohol.

The amount of the lubricant (Y) is 0.001 to 2 parts by mass relative to 100 parts by mass of the resin mixture (M). The amount of the lubricant (Y) relative to 100 parts by mass of the resin mixture (M) is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.12 parts by mass More than. In addition, the amount of the lubricant (Y) is preferably 1 part by mass or less relative to 100 parts by mass of the resin mixture (M), and more preferably 0.5 part by mass or less. When it is less than 0.001 parts by mass, the effect of the above-mentioned lubricant (Y) becomes insufficient, and even more than 2 parts by mass, the further effect of the above-mentioned lubricant (Y) cannot be obtained. The slip agent oozes from the molded product and sticks to the surface of the molded product. The lubricant (Y) can be used alone or in combination of two or more. As the lubricant (Y), when a plurality of lubricants (Y) having a difference in melting point of 5° C. or more are used, it is preferable because they can exhibit effects such as friction reduction in a wider temperature range.

Examples of the higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. From the viewpoint of high friction reduction and less mold contamination or roll contamination, the higher alcohol used in the present invention is preferably an aliphatic monohydric alcohol, more preferably an aliphatic monohydric alcohol having 12 to 18 carbon atoms, and still more preferably It is a saturated aliphatic monohydric alcohol having 12 to 18 carbon atoms, and more preferably a saturated aliphatic monohydric alcohol having 16 to 18 carbon atoms.

From the viewpoint of high friction reducing properties and high mold releasability, the aforementioned hydrocarbons are preferably aliphatic hydrocarbons having 12 or more carbon atoms. Further, aliphatic hydrocarbons such as flowing paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, etc.; partial oxides of aliphatic hydrocarbons; halogenated compounds of aliphatic hydrocarbons and the like can be used. Even in the case of such a commercially available mixture, the aliphatic hydrocarbon contained preferably has an average carbon number of 12 or more.

Examples of the aforementioned fatty acids include lauric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, tetracosanoic acid, oleic acid, erucic acid, arachidic acid, and 12-hydroxystearic acid. From the viewpoint of high friction reduction and less mold contamination or roll contamination, the fatty acid used in the present invention is preferably a fatty acid having 10 or more carbon atoms, more preferably a fatty acid having 16 to 24 carbon atoms, and even more preferably a carbon atom Number 16 to 24 of saturated fatty acids.

Examples of the aforementioned fatty acid metal salt include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexanoate, barium stearate, barium laurate, and barium ricinoleate. , Barium naphthenate, 2-ethyl Barium hexanoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexanoate, lead stearate, Binary lead stearate, lead naphthenate, tin stearate, aluminum stearate, magnesium stearate, etc.

From the viewpoint of high friction reduction and less mold contamination or roll contamination, fatty acids constituting fatty acid metal salts are preferably fatty acids having 10 or more carbon atoms, more preferably fatty acids having 16 to 24 carbon atoms, and further It is preferably a saturated fatty acid having 16 to 24 carbon atoms. From the viewpoint of stability and antifriction properties, the metal constituting the fatty acid metal salt preferably contains calcium, magnesium, zinc, lead, tin, iron, cadmium, aluminum, barium, cobalt, nickel, and manganese. , Strontium, titanium, vanadium, and copper, at least one metal, more preferably at least one metal selected from the group consisting of calcium, magnesium, zinc, and lead.

Examples of the aforementioned aliphatic amides include amide laurate, amide palmitate, amide stearate, amide arachidate, amide benzoate, amide oleate, amide eicosenoate, Erucyl erucate, erucyl amide, methylene bis-stearate amide, ethyl bis-stearate amide, etc. From the viewpoint of high friction reduction and less mold contamination or roll contamination, the aliphatic amides used in the present invention are preferably fatty acid amides having 12 or more carbon atoms, more preferably fatty acid amides having 16 to 22 carbon atoms , More preferably, it is an unsaturated fatty acid amide having 16 to 22 carbon atoms.

The aforementioned fatty acid ester (except lubricant (x1) + lubricant (x2)) refers to a fatty acid ester that does not have two or more hydroxyl groups in one molecule, and examples include fatty acid esters of monohydric alcohols and dihydric alcohols. Fatty acid esters, etc., specifically, diglyceride, triglyceride, acetylated monoglyceride, stearyl stearate, butyl stearate, ethylene glycol monostearate, ethyl Diol Distearate etc. Fatty acid esters used in the present invention (except for lubricant (x1) + lubricant (x2)), the number of carbon atoms of fatty acids in fatty acid esters from the viewpoint of high friction reduction and less mold contamination or roll contamination It is preferably 10 or more, and more preferably 16 to 24.

The lubricant of the present invention may further satisfy the following conditions (iii) and (iv). By satisfying (iii) and (iv), when the resin composition is melt-molded, no foreign matter defects or poor appearance are caused in the molded product.

(iii) Lubricant (x2) which does not contain lubricant (x2), or which is 0.1 parts by mass or less relative to 100 parts by mass of resin mixture (M); (iv) Lubricant (x1) and lubricant (x2) The total of is in the range of 0 to 0.1 with respect to 100 parts by mass of the resin mixture (M).

Within the range satisfying the condition (iv), the amount of the lubricant (x2) is preferably 0.05 parts by mass or less, more preferably 0.03 parts by mass or less, particularly preferably 100 parts by mass of the resin mixture (M). 0.01 parts by mass or less. When the amount of the lubricant (x2) is too large, a gel is generated when the resin composition is melt-molded, which tends to cause foreign matter defects or poor appearance of the molded product.

The resin composition system of the present invention may further contain various additives as necessary. Examples of the additives include heat stabilizers, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, inorganic fillers, inorganic fibers or organic fibers, polymer processing aids, antistatic agents, and Burning agents, dyes, colorants, matting agents, light diffusing agents, impact modifiers, phosphors, adhesives, adhesion-imparting agents, plasticizers, foaming agents, etc. The content of these additives can be appropriately set within a range that does not impair the effects of the present invention. For example, the resin composition 100 of the present invention Among the parts by mass, the content of the preferred antioxidant is 0.01 to 1.0 parts by mass, the content of the ultraviolet absorber is 0.01 to 3.0 parts by mass, and the content of the dye pigment is 0.00001 to 0.01 parts by mass.

The method of preparing the resin composition of the present invention is not particularly limited. For example, by kneading the resin mixture (M) at a temperature above the softening point and adding 100 parts by mass of the lubricant of the present invention to the resin mixture (M) satisfying the requirements (i) and (ii), the Additives and other polymers that need to be blended are obtained by kneading. Further, it can be obtained by dissolving the resin mixture (M), the lubricant satisfying the requirements (i) and (ii) of the present invention, additives that can be blended as needed, and other polymers in the solvent, and removing the solvent from the solution .

The glass transition temperature of the resin composition of the present invention is preferably 115 to 160°C. It is more preferably 130 to 155°C, and still more preferably 140 to 150°C. By setting the glass transition temperature of the resin composition in the range of 115 to 160°C, the balance of the heat resistance and impact resistance of the resin composition becomes good. For example, the resin composition and the thermoplastic resin such as polycarbonate The occurrence of warpage of the laminate under high temperature and high humidity is suppressed.

The saturated water absorption rate of the resin composition of the present invention in 23° C. water is preferably 0.3 to 1.9% by mass. It is more preferably 0.3 to 1.5% by mass, and still more preferably 0.3 to 1.0% by mass. By setting the saturated water absorption rate in the range of 0.3 to 1.9% by mass, it is possible to suppress the warpage of the laminate due to moisture absorption. In addition, the saturated water absorption is the value measured by immersing the molded product in distilled water at 23° C. and measuring the mass over time. The mass at equilibrium reaches an increase relative to the mass of the vacuum-dried molded product for 3 days or more rate.

The resin composition of the present invention is an extrusion molding method such as a co-extrusion molding method, a T-die lamination molding method, an extrusion coating method; an embedded injection molding method, a two-color injection molding method, a core-pull injection molding method, Injection molding methods such as interlayer injection molding, injection die-casting, etc.; blow molding; calendering; pressure molding; leaching molding, etc. are used to heat and melt-mold, whereby various molded products can be obtained. Even if the resin composition of the present invention is melt-molded at a high temperature for a long period of time, it is difficult to form a gel, and therefore it is also suitable for manufacturing a molded product requiring high temperature and long-term retention conditions. The resin composition of the present invention is suitable for the production of thin and wide molded products such as sheets, films, and plates.

[Laminate]

The layered system of the present invention has at least one layer composed of the resin composition of the present invention (hereinafter, also referred to as resin composition [C1]) and at least one layer composed of other materials. Other materials used in the laminate of the present invention are not particularly limited. Examples include organic materials such as resins, and inorganic materials such as metal monomers and metal oxides.

A layered system according to an embodiment of the present invention has at least one layer composed of a resin composition [C1] and at least one layer composed of a resin composition [C2] of another layer.

The resin system contained in the resin composition [C2] is not particularly limited. Examples of the resin include polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, and polyvinylidene chloride. Ethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, polysiloxane modified resin, polyether ether Ketones, polyphenols, polyphenylene oxides, polyimides, polyetherimides; thermosetting resins such as phenolic resins, melamine resins, polysiloxane resins, epoxy resins, etc.; energy line curing resins. The resin of the resin composition [C2] can be used individually by 1 type or in combination of 2 or more types. Among these, thermoplastic resin is preferable, and polycarbonate is more preferable.

When polycarbonate is used as the resin, the amount of polycarbonate contained in the resin composition [C2] is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. The weight average molecular weight of polycarbonate is preferably 20,000 to 100,000. When the weight average molecular weight of the polycarbonate is within the aforementioned range, the heat resistance and impact resistance of the resin composition [C2] are improved, and the resin composition [C1] can be manufactured with excellent moldability and high productivity Laminated sheet composed of resin composition [C2]. Moreover, the Mw/Mn of the polycarbonate is preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0.

Commercially available products can be used for the above-mentioned polycarbonate. For example, "Caliber (registered trademark)" manufactured by Sumitomo Styron Polycarbonate Co., Ltd., "Iupilon/Novarex (registered trademark)" manufactured by Mitsubishi Engineering Plastics Co., Ltd., "TARFLON (registered trademark)" manufactured by Idemitsu Kosei Co., Ltd., "Panlite (registered trademark)" manufactured by Teijin Chemical Co., Ltd., etc.

The resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a glass transition temperature of 130 to 160°C. The thermoplastic resin composition (T) is preferably a resin composition containing polycarbonate. In addition, it is preferable that the resin composition [C2] has a glass transition temperature that is approximately the same as the glass transition temperature of the resin composition [C1]. Specifically, resin The difference ΔTg between the glass transition temperature of the composition [C2] and the glass transition temperature of the resin composition [C1] is preferably 30° C. or lower, and more preferably 20° C. or lower. When the glass transition temperature of the two resins is 30° C. or lower, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity becomes higher.

The resin composition [C2] used in the present invention preferably has a saturated water absorption rate of 0.2 to 0.5% by mass. In addition, it is preferable that the resin composition [C2] has a saturation water absorption rate equal to that of the resin composition [C1]. Specifically, the difference between the saturated water absorption rate of the resin composition [C2] and the resin composition [C1], that is, the Δ saturated water absorption rate is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. When the saturated water absorption rates of the two resins are the same, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity becomes higher.

In order to improve thermal decomposition resistance, thermal discoloration resistance, light resistance, etc., the resin composition [C2] used in the present invention may contain well-known additives. Examples of additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes, and light diffusing agents. , Organic pigments, matting agents, impact-resistant modifiers, phosphors, etc.

A laminated system according to another embodiment of the present invention has at least one layer [L1] composed of a resin composition [C1], at least one layer [L2] composed of a resin composition [C2], and at least one layer The functional endowment layer [L3]. The function-imparting layer [L3] is not particularly limited. Examples thereof include a scratch-resistant layer, a hard coat layer, an antistatic layer, an antifouling layer, a friction reducing layer, an anti-glare layer, an anti-reflection layer, an adhesive layer, and an impact strength-imparting layer. The function-imparting layer [L3] can be formed by a well-known method. For example, hard coating It can be obtained by applying a resin solution for hard coating, and drying and hardening. The antireflection layer can be obtained by depositing a low-refractive index film and a high-refractive index film by vapor deposition or the like. Among the function-imparting layers [L3], for example, a scratch-resistant layer, a hard coat layer, an antistatic layer, an anti-fouling layer, a friction reducing layer, an anti-glare layer, an anti-reflection layer, etc. are usually provided on the outermost side of the laminate. The function-imparting layer [L3] may be provided with only one kind or a plurality of kinds. From the viewpoint of improving scratch resistance, the laminate of the present invention preferably has a scratch resistance layer on at least one surface.

The layer structure in the laminate of the present invention is not particularly limited. In terms of the stacking order of the layered product of the present invention, when the layer composed of the resin composition [C1] is marked as [L1] layer, the layer composed of the resin composition [C2] is marked as [L2] layer, function When the property-imparting layer [L3] is marked as "L3" layer, for example: [L1] layer/[L2] layer, [L1] layer/[L2] layer/[L1] layer, [L2] layer/[L1 ] Layer/[L2] layer/[L1] layer/[L2] layer/[L1] layer/[L2] layer/[L1] layer/[L1] layer/[L2] layer/[L3] layer/[L3 ] Layer/[L1] layer/[L2] layer, [L3] layer/[L1] layer/[L2] layer/[L3] layer, [L3] layer/[L1] layer/[L2] layer/[L1 ] Layer/[L3] layer, [L1] layer/[L2] layer/[L3] layer/[L2] layer/[L1] layer, etc. For example, when the [L3] layer is a hard coat layer, it is preferably [L3] layer/[L1] layer/[L2] layer, [L3] layer/[L1] layer/[L2] layer/[L3] Layer, [L3] layer/[L1] layer/[L2] layer/[L1] layer/[L3] layer.

The present invention is useful in laminates having shapes such as sheets, sheets, and films. When using the layered product of the present invention as a protective cover, it is preferable to arrange the resin composition [C1] layer so as to be positioned at the outermost side when viewed from the protected surface (protected surface). For example, it is preferable that the layered body composed of the [L1] layer/[L2] layer is composed of [L1] layer/[L2] layer /Protected surface is arranged in order, or the layered body composed of [L1] layer/[L2] layer/[L1] layer is composed of [L1] layer/[L2] layer/[L1] layer/cover Configure the protection plane in order.

The total thickness of the laminate of the present invention can be set according to the application, but it is preferably 0.2 to 2 mm, and more preferably 0.3 to 1.5 mm. If it is too thin, the rigidity tends to be insufficient. If it is too thick, it tends to hinder the weight reduction of liquid crystal display devices and the like.

The thickness of the layer composed of the resin composition [C1] in the laminate of the present invention is preferably in the range of 0.02 to 0.5 mm. The lower limit of the thickness of the layer is more preferably 0.03 mm or more, and still more preferably 0.05 mm or more. In addition, the upper limit of the thickness of the layer is more preferably 0.3 mm or less, and still more preferably 0.1 mm or less. When the thickness is less than 0.01 mm, there may be insufficient scratch resistance and weather resistance. When it exceeds 0.5 mm, the impact resistance may be insufficient.

From the viewpoint of suppressing the occurrence of warpage under high temperature and high humidity, the layered sheet of the present invention preferably makes the layering order symmetrical in the thickness direction, and more preferably the thickness of each layer also becomes symmetrical.

The laminate of the present invention is not particularly limited by its manufacturing method, and can be manufactured by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer pressure molding, multicolor injection molding, embedded injection molding, etc. . Among these multilayer molding methods, from the viewpoint of productivity, multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferred.

The method of multilayer extrusion molding is not particularly limited, and a well-known multilayer extrusion molding used in the manufacture of a multilayer laminate of thermoplastic resin can be used The method is, for example, forming by a device including a flat T-shaped mold and a polishing roller whose surface has been processed into a mirror surface. As for the method of the T-die, the resin block [C1] and the resin composition [C2] in the molten state before heating into the T-die can be fed by a feed block method or resin composition Multi-manifold system in which the material [C1] and the resin composition [C2] are stacked inside the T-die. From the viewpoint of improving the smoothness of the interface between the layers constituting the laminate, the multi-manifold method is preferred.

The resin composition [C1] and the resin composition [C2] are preferably melt-filtered with a filter before performing multilayer molding. By using each resin composition melt-filtered to form multiple layers, a laminated sheet with few defects from foreign matter, gel, etc. can be obtained. The filter used for melt filtration is not particularly limited. This filter system can be appropriately selected from well-known ones from the viewpoints of use temperature, viscosity, and required filtration accuracy. Specific examples of filters include nonwoven fabrics made of polypropylene, cotton, polyester, mucilage rayon, glass fiber, etc.; phenolic resin-impregnated cellulose film; metal fiber nonwoven sintered film; metal powder sintered film; metal mesh ; Or a combination of these. Among them, from the viewpoint of heat resistance, durability, and pressure resistance, it is preferable to use a plurality of laminated metal fiber nonwoven sintered films.

The filtering accuracy of the aforementioned filter is not particularly limited, but it is preferably 30 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less.

The resin composition of the present invention has excellent heat resistance and moisture resistance. In addition, when the molded product and the laminate are manufactured using the resin composition of the present invention, the adhesion to the forming roll and the mold release property are good, and the formation of gel can be effectively improved even by continuous melt molding for a long time. The molded product and the laminate formed by melt-molding the resin composition of the present invention have small dimensional changes, few foreign matter defects, and good appearance, and therefore can be suitably used for optical members and the like.

[Example]

The following shows examples and comparative examples to more specifically explain the present invention. However, the present invention is not limited to these embodiments.

[Resin composition]

The physical properties of the methacrylic resin (A) and the resin composition obtained in Production Examples, Examples 1a to 7a and Comparative Examples 1a to 4a were measured according to the following methods.

<glass transition temperature (Tg)>

According to JIS K7121, the resin composition of the present invention is heated from room temperature to 200°C at 20°C/min, held for 10 minutes, then cooled to room temperature, and then heated from room temperature to 200°C at 10°C/min Under the conditions, differential scanning calorimetry (DSC) was performed. The mid-point glass transition temperature determined from the DSC curve measured during the second temperature increase is adopted as the glass transition temperature in the present invention. As a measuring device, DSC-50 manufactured by Shimadzu Corporation was used.

<saturated water absorption>

Using an injection molding machine (made by Sumitomo Heavy Industries, Ltd., SE-180DU-HP), the resin composition of the present invention was injection molded under the conditions of a barrel temperature of 280°C, a mold temperature of 75°C, and a molding cycle of 1 minute. A square test piece with a thickness of 2 mm and a side of 50 mm was obtained. Under the conditions of a temperature of 80° C. and 5 mmHg, the test piece was vacuum dried for 24 hours. Next, the test piece was allowed to cool in a desiccator. Remove the test piece from the dryer and immediately measure the mass (initial mass).

Next, the test piece was immersed in distilled water at 23°C. Remove the test piece from the water, wipe off the water adhering to the surface and measure the mass. This test piece was immersed in distilled water, and the mass was measured in the same manner as described above. Repeat the immersion in distilled water and quality measurement until the quality no longer changes. The saturated water absorption rate is calculated from the mass (water absorption quality) and initial mass when the mass does not change by the following formula.

Saturated water absorption rate (%) = [(water absorption quality-initial quality) / initial quality] × 100

<Production Example 1>

In an autoclave, add 96.5 parts by mass of methyl methacrylate, 2.5 parts by mass of methyl acrylate, 0.06 parts by mass of azobisisobutyronitrile, 0.25 parts by mass of n-octyl mercaptan, and 250 parts by mass of water , 0.09 parts by mass of dispersant and 1.07 parts by mass of pH adjuster.

While stirring the inside of the autoclave, the temperature of the liquid was raised from room temperature to 70°C and kept at 70°C for 120 minutes to carry out the polymerization reaction. The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was withdrawn from the autoclave. The solid content was taken out from the polymerization reaction liquid by filtration, washed with water, and dried with hot air at 80°C for 24 hours to obtain a bead-shaped methacrylic resin with a glass transition temperature of 110°C and a saturated water absorption rate of 2.1% by mass [A] .

<Example 1a>

Melting and kneading 90 parts by mass of methacrylic resin (A) and 10 parts by mass of ethylene-based copolymer (B) (manufactured by Electric Chemical Industry Co., Ltd., RESISFY R- 200, glass transition temperature 134℃, saturated water absorption rate 0.7% by mass) and 0.15 parts by mass of cetyl alcohol (made by Kao Co., Ltd., KALCOL) as a lubricant (Y) 6098), 0.03 parts by mass of stearic acid monoglyceride (EXCEL T95 manufactured by Kao Corporation) as a lubricant (x1). Then, the molten resin is pressed to obtain a pellet-shaped resin composition [1]. Table 1 shows the composition and physical properties (Tg and saturated water absorption rate of the resin composition) of the resin composition [1].

<Example 2a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 70 parts by mass of methacrylic resin (A) and 30 parts by mass of ethylene-based copolymer (B). . Table 1 shows the composition and physical properties of the resin composition [2].

<Example 3a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 50 parts by mass of methacrylic resin (A) and 50 parts by mass of ethylene-based copolymer (B). . Table 1 shows the composition and physical properties of the resin composition [3].

<Example 4a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 30 parts by mass of methacrylic resin (A) and 70 parts by mass of ethylene-based copolymer (B). . Table 1 shows the composition and physical properties of the resin composition [4].

<Example 5a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 5 parts by mass of methacrylic resin (A) and 95 parts by mass of ethylene-based copolymer (B). . Table 1 shows the composition and physical properties of the resin composition [5].

<Example 6a>

A resin composition was obtained in the same manner as in Example 4a except that the amount of cetyl alcohol was changed to 0.3 [6]. Table 1 shows the composition and physical properties of the resin composition [6].

<Example 7a>

A resin composition was obtained in the same manner as in Example 4a except that the amount of stearic acid monoglyceride was changed to 0.05 parts by mass. Table 1 shows the composition and physical properties of the resin composition [7].

<Example 8a>

In addition to replacing stearic acid monoglyceride and adding 0.03 parts by mass of neopentaerythritol distearate (lubricant (x2) (manufactured by NOF Corporation, UNISTER H-476D) as a lubricant, the The resin composition [8] was obtained by the same method as in Example 4a. The composition and physical properties of the resin composition [8] are shown in Table 1.

<Example 9a>

A resin composition was obtained in the same manner as in Example 4a except that a lubricant (Y) containing only 0.15 parts by mass of cetyl alcohol was used as a lubricant [9]. Table 1 shows the composition and physical properties of the resin composition [9].

<Example 10a>

A resin composition was obtained in the same manner as in Example 4a, except that 0.05 part by mass of stearyl alcohol (manufactured by Kao Corporation, KALCOL 8098) was added as a lubricant (Y). Table 1 shows the composition and physical properties of the resin composition [10].

<Example 11a>

A resin composition was obtained in the same manner as in Example 4a except that stearyl alcohol was used as the lubricant (Y) instead of cetyl alcohol [11]. Will tree The composition and physical properties of the fat composition [11] are shown in Table 1.

<Example 12a>

A resin composition was obtained in the same manner as in Example 4a except that stearic acid (manufactured by Kao Corporation, LUNAC S-90V) was used instead of cetyl alcohol as the lubricant (Y). Table 1 shows the composition and physical properties of the resin composition [12].

<Example 13a>

A resin was obtained in the same manner as in Example 4a except that instead of cetyl alcohol, N,N'-methylenebisstearate amide (Bisamide LA, manufactured by Nippon Kasei Co., Ltd.) was used as the lubricant (Y). Composition [13]. Table 1 shows the composition and physical properties of the resin composition [13].

<Example 14a>

A resin composition was obtained in the same manner as in Example 4a except that low molecular weight polyethylene (Sanwa Chemical Industry Co., Ltd., Sunwax 15-P) was used instead of cetyl alcohol as the lubricant (Y). Table 1 shows the composition and physical properties of the resin composition [14].

<Comparative Example 1a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 95 parts by mass of methacrylic resin (A) and 5 parts by mass of ethylene-based copolymer (B). . Table 1 shows the composition and physical properties of the resin composition [15].

<Comparative Example 2a>

A resin composition was obtained in the same manner as in Example 1a except that the composition ratio of the resin mixture (M) was 3 parts by mass of methacrylic resin (A) and 97 parts by mass of ethylene-based copolymer (B). . Resin composition The composition and physical properties of the substance [16] are shown in Table 1.

<Comparative Example 3a>

A resin composition was obtained in the same manner as in Example 3a except that the amount of stearic acid monoglyceride of the lubricant (x1) was changed to 0.15 parts by mass. Table 1 shows the composition and physical properties of the resin composition [17].

<Comparative Example 4a>

A resin composition was obtained in the same manner as in Example 3a except that no lubricant was used [18]. Table 1 shows the composition and physical properties of the resin composition [18].

As shown in the above results, the resin composition of the present invention (Examples 1a to 14a) has a high glass transition temperature and a low saturation water absorption rate, and therefore has excellent heat resistance and moisture resistance.

[Laminate]

In a single-shaft extruder [I] (Toshiba Machinery Co., Ltd.) equipped with a vent hole with a shaft diameter of 150 mm set to a cylinder temperature of 245 to 260°C and a discharge volume of 430 kg/hour, polycarbonate ( Pills of "SD POLYCA (registered trademark) PCX" manufactured by Sumiron Polycarbonate Co., Ltd.). In a single-shaft extruder [II] (Toshiba Machinery Co., Ltd.) equipped with a cylinder temperature of 215 to 230°C and a discharge volume of 37 kg/hour with a vent hole having a shaft diameter of 65 mm, examples and comparisons were continuously put in Examples of pellets of resin composition.

Simultaneously extrude polycarbonate and resin composition from extruder [I] and extruder [II], and pass through a folded cylindrical filter with a pore size of 15 μm pre-filled with resin (Fuji Filter Industry Co., Ltd. After it is manufactured by the company, it is introduced into a junction block, followed by co-extrusion molding of polycarbonate using a multi-manifold die (Nordson Co., Ltd.) with a resin discharge width of 1600 mm and a lip interval of 2.0 mm at a temperature of 230 to 245°C. With resin composition.

The laminates obtained in Examples 1b to 14b and Comparative Examples 1b to 4b were evaluated by the following methods.

<Appearance>

Under the following extrusion conditions, the laminate obtained after 15 hours of continuous operation was visually observed and the number of gel-like foreign matter defects was counted. The gel-like foreign matter defect refers to a high-molecular weight body of a resin composition exhibiting transparency, which disturbs the interface layer of the laminate and is calculated as a defect. Within an area of 2 m ² , the average number of defects is less than two, which is Good, and two or more are Poor.

<Formability>

The surface of the resin mixture (M) side of the laminate was visually observed, and checked for the presence of step-shaped defects (release marks) orthogonal to the extrusion flow direction. In the range of 30 cm in the extrusion flow direction, all or substantially unrecognizable step-like defects are good (Good), and those that do not conform to the aforementioned Good are poor (Poor).

<Amount of warpage change>

A rectangular test piece having a short side of 65 mm and a long side of 110 mm was cut from the laminate so that the direction perpendicular to the extrusion flow direction became the short side and the direction parallel to the extrusion flow direction became the long side. The short side of the hanging test piece was placed in an environmental testing machine set at a temperature of 75°C and a relative humidity of 50%. After being left for 4 hours, the test piece was cooled to 25°C. As a result, the test piece was bent into an arch shape. Place the test piece bent into an arch shape on the platform in such a way that the end of the test piece contacts the platform (that is, in such a way that the test piece is mountain-shaped), using a gap gauge to determine the difference between the platform and the test piece The maximum distance between spaces (usually the maximum value near the center of the long side of the test piece). Use this value as the initial warpage.

Next, the short side of the test piece bent in an arch shape was suspended, and left for 72 hours in an environmental testing machine set at a temperature of 85° C. and a relative humidity of 85%. After the test piece was allowed to cool for 4 hours in an environmental testing machine set at 25°C and a relative humidity of 50%, the maximum distance between the platform and the test piece was measured in the same manner as described above. The difference between this measured value and the initial warpage amount is defined as the "warpage change amount". A change in warpage of 1.0 mm or less is good (Good), and a change in warpage of more than 1 mm is poor (Poor).

<scratch resistance>

The measurement was performed using a tabletop mobile pencil scratch tester (Type P) (manufactured by Toyo Seiki Co., Ltd.). On the surface of the layer including the resin mixture (M) of the laminate obtained in Examples and Comparative Examples, while pressing the core of the pencil at an angle of 45 degrees and a load of 750 g, the presence or absence of scratches was confirmed. The hardness of the core of the pencil is gradually increased, and the hardness of the core that is softer than the time when the scratch is generated is regarded as scratch resistance. Those with scratch resistance of F or more are good (Good), and those with less than F are poor (Poor).

<Example 1b>

In a single-screw extruder [I] set at a cylinder temperature of 245 to 260°C and a discharge volume of 430 kg/hour with a shaft diameter of 150 mm, polycarbonate was continuously introduced ("SD POLYCA" manufactured by Sumitomo Styron Polycarbonate Co., Ltd. Registered trademark) PCX". The same below) pellets. The pellets of the resin composition [1] were continuously put into a uniaxial extruder [II] set at a cylinder temperature of 215 to 230°C and a discharge volume of 37 kg/hour with a shaft diameter of 65 mm.

Simultaneously extrude polycarbonate and resin composition [1] from extruder [I] and extruder [II], and pass through a folded cylindrical filter with a filter pore size of 15 μm prefilled with resin (Fuji Filter Industry) (Manufactured by a company limited by shares), then introduced into the joining section, and then the polycarbonate and the resin composition were mixed using a resin manifold (1600 mm wide, lip spacing 2.0 mm, multi-manifold mold (Nordson Co., Ltd.)) at a temperature of 245°C [1] Co-extruded to form flakes. The sheet was bank-molded between No. 1 and No. 2 rolls of four rolls in the transverse direction, and cooled with the transfer of the mirror surface using the four rolls to obtain a resin composition [1] containing a thickness of 80 μm. A layered body with a total thickness of 1000 μm and a layer made of polycarbonate with a thickness of 920 μm.

<Example 2b>

Except that the resin composition [1] was changed to the resin composition [2], in the same manner as in Example 1b, a layer composed of the resin composition [2] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 3b>

Except that the resin composition [1] was changed to the resin composition [3], in the same manner as in Example 1b, a layer composed of the resin composition [3] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 4b>

Except that the resin composition [1] was changed to the resin composition [4], in the same manner as in Example 1b, a layer composed of the resin composition [4] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 5b>

Except that the resin composition [1] was changed to the resin composition [5], in the same manner as in Example 1b, a layer composed of the resin composition [5] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm composed of layers.

<Example 6b>

Except that the resin composition [1] was changed to the resin composition [6], in the same manner as in Example 1b, a layer composed of the resin composition [6] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 7b>

Except that the resin composition [1] was changed to the resin composition [7], in the same manner as in Example 1b, a layer composed of the resin composition [7] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 8b>

Except that the resin composition [1] was changed to the resin composition [8], in the same manner as in Example 1b, a layer composed of the resin composition [8] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 9b>

Except that the resin composition [1] was changed to the resin composition [9], in the same manner as in Example 1b, a layer composed of the resin composition [9] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 10b>

Except that the resin composition [1] was changed to the resin composition [10], in the same manner as in Example 1b, a layer composed of the resin composition [10] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 11b>

Except that the resin composition [1] was changed to the resin composition [11], in the same manner as in Example 1b, a layer composed of the resin composition [11] with a thickness of 80 μm and a polycarbonate made of polycarbonate with a thickness of 920 μm were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 12b>

Except that the resin composition [1] was changed to the resin composition [12], in the same manner as in Example 1b, a layer consisting of the resin composition [12] with a thickness of 80 μm and a polycarbonate made with polycarbonate with a thickness of 920 μm were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 13b>

Except that the resin composition [1] was changed to the resin composition [13], in the same manner as in Example 1b, a layer composed of the resin composition [13] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Example 14b>

Except that the resin composition [1] was changed to the resin composition [14], in the same manner as in Example 1b, a layer composed of the resin composition [14] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Comparative Example 1b>

Except that the resin composition [1] was changed to the resin composition [15], in the same manner as in Example 1b, a layer composed of the resin composition [8] with a thickness of 80 μm and a polycarbonate made of polycarbonate with a thickness of 920 μm were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Comparative Example 2b>

Except that the resin composition [1] was changed to the resin composition [16], in the same manner as in Example 1b, a layer consisting of the resin composition [9] with a thickness of 80 μm and a polycarbonate with a thickness of 920 μm were obtained The laminate has a total thickness of 1000 μm.

<Comparative Example 3b>

Except that the resin composition [1] was changed to the resin composition [17], in the same manner as in Example 1b, a layer composed of the resin composition [9] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

<Comparative Example 4b>

Except that the resin composition [1] was changed to the resin composition [18], in the same manner as in Example 1b, a layer composed of the resin composition [10] having a thickness of 80 μm and a polycarbonate composed of 920 μm in thickness were obtained. A layered body with a total thickness of 1000 μm constituting the layer.

Table 2 shows the evaluation results of Examples 1b to 14b and Comparative Examples 1b to 4b.

As shown in the above results, it is known that the laminates of the present invention (Examples 1b to 14b) have fewer foreign matter defects such as gels generated during long-term melt-molding and less mold release marks. Furthermore, known Mingzhi's laminate has excellent scratch resistance, and even if left under high temperature and high humidity, it has less warpage.

[Industry availability]

Examples of uses of the molded products, molded products, and laminates of the present invention include: advertising towers, standing signboards, outdoor signboards (side signboards), door signboards, roof signboards, and other signboard parts; display cabinets, partition boards , Shop display and other display parts; fluorescent lampshade, atmosphere lighting lampshade, lampshade, luminous ceiling, light wall, chandelier and other lighting parts; pendant, mirror and other interior decoration parts; doors, vaults, safety glass windows, partition walls, stair protection , Balcony walls, roofs for leisure buildings and other building parts; aircraft windshields, pilot sunshades, motorcycles, motorboat windshields, bus sunshades, car sunshades, rear sunshades, front wing, front Lamps, lampshades and other transportation-related parts; audio and video signs, stereo housings, TV protection covers, vending machine display covers, and other electronic machine parts; thermal insulation boxes, X-ray parts and other medical equipment parts; mechanical housings, instrument covers, Experimental devices, scales, dials, observation windows and other machine-related parts; LCD protective plates, light guide plates, light guide films, Fresnel lenses, lenticular lenses, front panels of various displays, diffusion plates and other optical related parts; road signs, Traffic-related parts such as guide plates, curved mirrors, soundproof walls, etc.; film materials such as surface materials for automotive interiors, mobile phone surface materials, marking films, etc.; upper cover materials for washing machines and control panels, top panels for rice cookers, and other household appliances Components for products; others, greenhouses, large sinks, box sinks, clock panels, bathtubs, sanitary equipment, table mats, game parts, toys, masks for face protection during welding, etc.

Claims (14)

A resin composition containing a resin mixture (M) and a lubricant, the resin mixture (M) containing 5 to 90% by mass of methacrylic resin (A), and 10 to 95% by mass of at least The structural unit of the aromatic vinyl compound (b1) represented by the formula (1) is 50% by mass or more and 84% by mass or less and the structural unit derived from the cyclic acid anhydride (b2) represented by the following general formula (2) is 18% by mass Above 49% by mass or less of ethylene-based copolymer (B), the lubricant satisfies the following conditions (i) to (iv): (i) does not contain monoglycerides containing saturated fatty acids having 10 to 24 carbon atoms Lubricant (x1) or a lubricant (x1) containing 0.1 to 10 parts by mass or less of monoglyceride of a saturated fatty acid having 10 to 24 carbon atoms relative to 100 parts by mass of the resin mixture (M); (ii) Relative to 100 parts by mass of the resin mixture (M), 0.001 to 2 parts by mass is selected from the group consisting of higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, and fatty acid esters (wherein, the lubricant (x1 ), and lubricants other than the lubricant (x1) containing at least one fatty acid ester having two or more hydroxyl groups in one molecule (except for lubricants (x2))) (Y); (iii) No Lubricant (x2) containing lubricant (x2) or 0.1 parts by mass or less relative to 100 parts by mass of resin mixture (M); (iv) The total of lubricant (x1) and lubricant (x2) is relative In the range of 0 to 0.1 parts by mass for 100 parts by mass of the resin mixture (M),

(R ¹ and R ² in the formula each independently represent a hydrogen atom or an alkyl group);

(R ³ and R ⁴ in the formula each independently represent a hydrogen atom or an alkyl group). The resin composition according to claim 1, wherein the lubricant (Y) is at least one selected from the group consisting of an aliphatic monohydric alcohol having 12 to 18 carbon atoms and a saturated fatty acid having 16 to 24 carbon atoms. The resin composition according to claim 1 or 2, wherein the resin mixture (M) contains 30 to 60% by mass of methacrylic resin (A) and 40 to 70% by mass of ethylene-based copolymer (B). The resin composition according to claim 1 or 2, wherein the ethylene-based copolymer (B) contains 50 to 84% by mass of structural units derived from the aromatic vinyl compound (b1), and contains 15 to 49% by mass of cyclic anhydride The structural unit of (b2) contains 1 to 35% by mass of the structural unit derived from methacrylate (b3). The resin composition according to claim 4, wherein the methacrylate (b3) is methyl methacrylate. The resin composition according to claim 1 or 2, wherein the glass transition temperature is 115 to 160°C. The resin composition as claimed in claim 1 or 2, in which the saturation in water at 23°C The water absorption rate is 0.3 to 1.9% by mass. The resin composition according to claim 1 or 2, wherein the lubricant does not contain a lubricant (x1) for this (i), and does not contain a lubricant (x2) for this (iii). The resin composition according to claim 1 or 2, wherein the total amount of the lubricant is 0.1 part by mass or more relative to 100 parts by mass of the resin mixture (M). A molded product provided with the resin composition according to any one of claims 1 to 9. A laminate including a layer composed of the resin composition according to any one of claims 1 to 9 and a layer composed of a thermoplastic resin composition (T) having a glass transition temperature in the range of 130 to 160°C. The laminate according to claim 11, wherein the thermoplastic resin composition (T) is a polycarbonate-containing resin composition. The laminate according to claim 11 or 12, wherein the difference between the glass transition temperature of the thermoplastic resin composition (T) and the resin composition is 30°C or less. The laminate according to claim 11 or 12, further has a scratch-resistant layer on at least one surface.