JP2003128825A - Blow molding resin composition and blow molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-slip blow molding resin composition which has ideal fitting properties itself and can be used for various applications without particularly applying lamination or coating, and to provide a blow molded article prepared therefrom. SOLUTION: The blow molding resin composition comprises a graft copolymer in which at least one vinyl monomer copolymerizable with a rubber polymer is grafted at least to the rubber polymer, and a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes good use of the non-slip property of a foam-molded resin composition having a non-slip property, a foam resin molded product such as a non-slip foam resin sheet, and more specifically, a rubber-based graft copolymer. The present invention relates to a resin composition for foam molding and has various uses such as building materials, packaging, and automobile interiors.

[0002]

2. Description of the Related Art As is well known, foamed molded articles made of thermoplastic resin have excellent heat insulating properties and soundproofing properties. Therefore, in the field of construction, as floor coverings for silent floors, or as soundproofing / insulating materials, Further, in the field of packaging as well, as a cushioning material for preventing damage to transportation articles, the weight can be significantly reduced as compared with an unfoamed product, so that demand for automobile interiors is expanding. However, conventionally, in order to impart a fit property (anti-slip property) to a foamed resin molded article, it is disclosed in Japanese Patent Laid-Open No.
Nos. 37660 and 10-211081, a resin having a good fit property on the surface of the foamed resin is bonded at the time of molding the foamed resin or after molding,
It was necessary to separately process such as applying an adhesive.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to overcome the above-mentioned problems in conventional foamed resin molded articles, and is specially subjected to a laminating process or a coating process in order to obtain a fit property. It is an object of the present invention to provide a resin composition for foam molding, in which the resin itself has an ideal fit property, and a foamed resin molded article made from the composition, even if the resin itself does not exist.

[0004]

In order to solve the above-mentioned problems, a rubber-based polymer is added with a graft copolymer obtained by graft-polymerizing at least one vinyl monomer into a thermoplastic resin, followed by foam molding. As a result, they have found that the fit of the obtained foamed resin molded product is improved, and the present invention has been completed.

The present invention relates to a foam molding resin containing at least a rubber-like polymer, a graft copolymer obtained by graft-polymerizing at least one vinyl monomer copolymerizable therewith, and a thermoplastic resin. In composition.

Further, in the present invention, in the above foam molding resin composition, the graft copolymer and a thermoplastic resin of the same kind as the above thermoplastic resin or another thermoplastic resin dispersed in the thermoplastic resin are melt-mixed in advance. A resin composition for foam molding, comprising a pellet-shaped masterbatch added to the thermoplastic resin.

The present invention also relates to a foam sheet, which is a non-slip foam resin molded product characterized by foam-molding the above resin composition for foam molding.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer used in the graft copolymer used in the resin composition for foam molding of the present invention includes diene rubber polymers, acrylic rubber polymers and silicone / acrylic rubbers. Polymers may be mentioned.

First, the diene rubber polymer used in the graft copolymer used in the present invention will be described. The diene rubber polymer is a polymer obtained by homopolymerization of diene monomers or copolymerization with other monomers, and 50 to 100% by mass of 1,3 butadiene and a vinyl monomer copolymerizable therewith. It is preferable to use a butadiene rubber polymer obtained by emulsion polymerization of 0 to 50 mass%.

Examples of vinyl monomers used for forming the diene rubber polymer include styrene, aromatic vinyl such as α-methylstyrene, methyl methacrylate, and the like.
Methacrylic acid alkyl ester such as ethyl methacrylate, ethyl acrylate, acrylic acid alkyl ester such as n-butyl acrylate, unsaturated nitrile such as acrylonitrile and methacrylonitrile, vinyl ether such as methyl vinyl ether and butyl vinyl ether, vinyl chloride, vinyl bromide, etc. And vinylidene halides such as vinylidene chloride, vinylidene chloride and vinylidene bromide, and vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and ethylene glycol glycidyl ether.

The vinyl-based monomer may be crosslinkable. The crosslinkable vinyl-based monomer may be any that can be copolymerized with the vinyl-based monomer, for example,
Aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, ethylene glycol dimethacrylate,
Polyhydric alcohols such as 1,3 butanediol diacrylate, trimethacrylic acid esters and / or triacrylic acid esters, allyl esters of carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl phthalate, diallyl sebacate, triallyl triazine, etc. And di- and tri-allyl compounds.

The vinyl-based monomer and the crosslinkable monomer are
One kind or two or more kinds can be used. The composition ratio of the components constituting the diene rubber polymer is within the above range, and if it deviates from these ranges, the non-slip property of the foamed resin molded product obtained using the same tends to decrease. In addition, when forming the rubber polymer, if necessary, t
Chain transfer agents such as dodecyl mercaptan can also be used.

To these diene rubber polymers, a thickening agent can be added if necessary. Examples of the thickening agent include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate and aluminum sulfate, organic salts such as calcium acetate and magnesium acetate, inorganic acids such as sulfuric acid and hydrochloric acid, acetic acid and succinic acid. And organic acid anhydrides thereof, carboxylic acid-containing polymer latexes, and the like.

The graft copolymer constituting the resin composition for foam molding of the present invention comprises at least one vinyl monomer which is copolymerizable in the presence of the butadiene rubber polymer latex having the above-mentioned constitution. It can be obtained by graft polymerization with this in a single stage or multiple stages.

Examples of the graft-polymerizable vinyl monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methylmethacrylate, 2
-Methacrylic acid esters such as ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, n-
Acrylic esters such as butyl acrylate; various vinyl-based monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. At least one monomer selected from these monomers should be used. You can Among these vinyl monomers, methyl methacrylate, butyl acrylate, acrylonitrile and styrene are preferably used.

The amount of the monomer or monomer mixture used for the graft polymerization is the acrylic rubber polymer latex 20.
It is preferably in the range of 10 to 80 parts by mass with respect to 90 parts by mass (as solid content). Graft polymerization may be carried out by adding a monomer or a mixture of monomers at one time, or by adding the monomer or mixture of monomers in two or more portions, the graft polymerization may be carried out in multiple stages. It can also be done separately.

Both rubber polymerization and graft polymerization are produced by emulsion polymerization. As a polymerization initiator for producing a graft copolymer resin, potassium persulfate, ammonium persulfate, persulfate such as sodium persulfate and t-butyl are used. Hydroperoxide, cumene hydroperoxide,
Organic peroxides such as benzoyl peroxide, lauroyl peroxide and diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile can be used. In addition, the above compound may be used in combination with a sulfite salt, a hydrogen sulfite salt, a thiosulfate salt, a first metal salt, sodium formaldehyde sulfoxylate, dextrose or the like as a redox initiator.

The rubber polymerization and graft copolymerization can be appropriately carried out at a temperature in the range of about 40 to 80 ° C., depending on the kind of the polymerization initiator. As the emulsifier, a known emulsifier can be appropriately used.

The obtained graft copolymer resin is spray-dried (directly powdered) with or without addition of an appropriate antioxidant or additive, or sulfuric acid, hydrochloric acid, phosphoric acid, etc. Acid, calcium chloride, coagulant such as salt of sodium chloride, etc. is used as appropriate, coagulated by heat treatment to solidify, dehydrated, washed and dried to obtain powdery diene rubber graft copolymer. To be done.

Next, the acrylic rubber graft copolymer using the acrylic rubber polymer used in the present invention will be explained. The rubber polymer that constitutes the acrylic rubber graft copolymer is a polymer obtained by homopolymerization of an acrylic monomer or copolymerization with another monomer. It is preferable to use an acrylic rubber polymer obtained by emulsion polymerization of 0 to 50 mass% of a copolymerizable vinyl monomer.

The acrylic ester used for forming the acrylic rubber polymer has an alkyl group having 2 carbon atoms.
Examples of the acrylic acid alkyl ester of 8 to 8 include ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Examples of vinyl monomers copolymerizable with these acrylic esters include styrene, aromatic vinyl such as α-methylstyrene, methacrylic acid alkyl esters such as methylmethacrylate and ethylmethacrylate, unsaturated acrylonitrile and methacrylonitrile, and the like. Vinyl ether such as nitrile, methyl vinyl ether, butyl vinyl ether, vinyl chloride,
Vinyl halides such as vinyl bromide, vinylidene chloride, vinylidene halides such as vinylidene bromide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl monomers having a glycidyl group such as ethylene glycol glycidyl ether, and the like. .

The vinyl monomer may be crosslinkable. The crosslinkable vinyl-based monomer is one that can be copolymerized with the above-mentioned vinyl-based monomer, and examples thereof include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, ethylene glycol dimethacrylate, and 1,3-butanediol. Polyhydric alcohol such as diacrylate, trimethacrylic acid ester, or allyl ester of carboxylic acid such as triacrylic acid ester, allyl acrylate, allyl methacrylate, diallyl phthalate, diallyl sebacate, diaryl such as triallyl triazine and the like. Triallyl compounds and the like can be mentioned.

The vinyl-based monomer and the crosslinkable vinyl-based monomer may be used either individually or in combination of two or more. The composition ratio of the constituents of the rubber polymer is within the above-mentioned range, and if it deviates from these ranges, the non-slip property of the foamed resin molded article obtained by using this tends to decrease. Further, when forming the rubber polymer, t-
Chain transfer agents such as dodecyl mercaptan can also be used.

The graft copolymer resin used in the present invention is a monomer having methyl methacrylate as an essential component in the presence of the acrylic rubber polymer latex having the above-mentioned composition, or at least one other monomer. It can be obtained by carrying out a one-step or multi-step graft polymerization of a monomer mixture composed of a copolymerizable vinyl monomer.

In the present invention, the vinyl-based monomer that can be graft-polymerized to the acrylic rubber includes aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; methyl methacrylate, 2-ethylhexyl methacrylate and the like. Methacrylic acid ester; acrylic acid ester such as methyl acrylate, ethyl acrylate, n-butyl acrylate; acrylonitrile,
Various vinyl-based monomers such as vinyl cyanide compounds such as methacrylonitrile may be mentioned, and at least one monomer selected from these monomers may be used. Among these vinyl monomers, methylmethacrylate,
Butyl acrylate, acrylonitrile, and styrene are preferably used.

The amount of the monomer or monomer mixture used in the graft polymerization is the acrylic rubber polymer latex 20.
It is preferably in the range of 10 to 80 parts by mass with respect to 90 parts by mass (as solid content). Graft polymerization may be carried out by adding a monomer or a mixture of monomers at one time, or by adding the monomer or mixture of monomers in two or more portions, the graft polymerization may be carried out in multiple stages. It can also be done separately.

Both rubber polymerization and graft polymerization are produced by emulsion polymerization. As a polymerization initiator for producing a graft copolymer resin, potassium persulfate, ammonium persulfate, persulfate such as sodium persulfate, and t-butyl are used. Hydroperoxide, cumene hydroperoxide,
Organic peroxides such as benzoyl peroxide, lauroyl peroxide and diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile can be used. In addition, the above compound may be used in combination with a sulfite salt, a hydrogen sulfite salt, a thiosulfate salt, a first metal salt, sodium formaldehyde sulfoxylate, dextrose or the like as a redox initiator. The polymerization can be appropriately performed within the range of about 40 to 80 ° C., though it depends on the kind of the polymerization initiator. A known emulsifier can be appropriately used as the emulsifier.

The graft copolymer resin thus obtained is spray-dried (directly powdered) with or without the addition of suitable antioxidants and additives, or with sulfuric acid, hydrochloric acid, phosphoric acid, etc. A coagulant such as an acid or a salt such as calcium chloride or sodium chloride is appropriately used for coagulation, heat treatment to solidify, dehydration, washing and drying to obtain a powdery acrylic rubber graft copolymer. .

Next, as the silicone / acrylic rubber polymer used in the present invention, a composite rubber composed of a polyorganosiloxane and an alkyl (meth) acrylate rubber can be used. The two components that make up the composite rubber are
Polyorganosiloxane rubber component is 1 to 99% by mass, polyalkyl (meth) acrylate component is 99 to 1% by mass.
(However, the total amount of both components is preferably 100% by mass).

The above-mentioned composite rubber may be manufactured by any method, but the emulsion polymerization method is most suitable. First, a latex of polyorganosiloxane is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate is prepared. It is preferable to impregnate the particles of the polyorganosiloxane latex with the monomer and then polymerize the monomer for synthesis.

The polyorganosiloxane rubber component constituting the above composite rubber can be prepared by emulsion polymerization using the following organosiloxane and cross-linking agent (a), in which case a graft crossing agent (b) is further added. It can also be used together.

As the organosiloxane, various cyclic compounds having three or more membered rings can be mentioned, and preferably 3 is used.
~ 6-membered ring. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These may be used alone or in combination of two or more. The amount of these used is 5 in the polyorganosiloxane component.
It is 0 mass% or more, preferably 70 mass% or more.

The cross-linking agent (a) may be trifunctional or tetrafunctional.
Functional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, etc. are used. Especially 4
Functional crosslinking agents are preferred, of which tetraethoxysilane is particularly preferred. The amount of the crosslinking agent used is 0.1 to 30% by mass in the polyorganosiloxane component.

As the graft crossing agent (b), a compound capable of forming a unit represented by the following formula is used. _{CH 2 = C (R 2)} -COO- (CH 2) p -SiR 1n O (3-n) / 2 (b-1) CH 2 = C (R 2) -C 6 H 4 -SiR 1n O ( _{3-n) / 2 (b} -2) CH 2 = CH-SiR 1n O (3-n) / 2 (b-3) HS- (CH 2) p -SiR 1n O (3-n) / 2 ( b-4) (In the formula, R ₁ is a methyl group, an ethyl group, a propyl group or a phenyl group, R ₂ is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number of 1 to 6. .)

The (meth) acryloyloxysiloxane capable of forming the unit of the above formula (b-1) has a high grafting efficiency and therefore can form an effective graft chain, and the resin composition for foam molding of the present invention. It is advantageous in that impact resistance of a molded product using the product is exhibited.

Methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the above formula (b-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl. Examples thereof include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and γ-methacryloyloxybutyldiethoxymethylsilane.

Vinyl siloxane is mentioned as a substance capable of forming the unit of the above formula (b-2), and specific examples thereof include:
Examples include tetramethyltetravinylcyclotetrasiloxane. Examples of the unit capable of forming the unit of the above formula (b-3) include p-vinylphenyldimethoxymethylsilane. Further, as a unit capable of forming the unit of the formula (b-4), γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane,
γ-mercaptopropyldiethoxymethylsilane and the like can be mentioned.

The amount of the graft crossing agent (b) used is 0 to 10% by mass, preferably 0.5 to 5% by mass in the polyorganosiloxane component.

The latex of the polyorganosiloxane component can be produced by the method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725. In the present invention, for example, an organosiloxane, a cross-linking agent (a), and optionally a mixed solution of a graft crossing agent (b) are mixed with, for example, a homogenizer in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferably produced by a method of shear mixing with water. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of organosiloxane and at the same time serves as a polymerization initiator.
At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization.

The polyalkyl (meth) acrylate component constituting the above composite rubber is an alkyl (meth) acrylate shown below.
It can be synthesized using an acrylate, a cross-linking agent and a graft crossing agent.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate and hexyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylates such as n-lauryl methacrylate, and the like, and the use of n-butyl acrylate is particularly preferable.

Examples of the above-mentioned crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crossing agent described above include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a cross-linking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the cross-linking agent and the graft crossing agent used is preferably 0.1 to 20 mass% in the polyalkyl (meth) acrylate component.

Polymerization of the polyalkyl (meth) acrylate component is carried out by adding the above alkyl (meth) acrylate into a latex of the polyorganosiloxane component neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate. After adding a crosslinking agent and a graft crossing agent and impregnating the polyorganosiloxane particles,
It is carried out by using a normal radical polymerization initiator. A latex of a composite rubber of a polyorganosiloxane component and a polyalkyl (meth) acrylate component is obtained as the polymerization proceeds.

In carrying out the present invention, the main skeleton of the polyorganosiloxane rubber component as the composite rubber has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate component is n-butyl acrylate. A composite rubber having a repeating unit is preferably used.

The silicone / acrylic rubber polymer thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer and has a gel content measured by extraction with toluene at 90 ° C. for 4 hours. It is preferably 80% by mass or more.

As the vinyl-based monomer which can be graft-polymerized to the above-mentioned silicone / acrylic rubber, styrene,
Aromatic alkenyl compounds such as α-methylstyrene and vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; acrylonitrile and methacrylonitrile. Various vinyl-based monomers such as vinyl cyanide compounds can be mentioned, and at least one monomer selected from these monomers can be used. Among these vinyl monomers, methyl methacrylate, butyl acrylate, acrylonitrile and styrene are preferably used. The amount of the monomer or monomer mixture used in the graft polymerization is 30% by weight of the silicone / acrylic rubber.
It is preferably 5 to 70 parts by mass with respect to ˜95 parts by mass.

Among the various graft copolymers mentioned above, those produced by emulsion polymerization are obtained in the state of latex. Therefore, various means are used for solidification. Generally, it can be obtained as a powder produced by a rapid solidification method using an acid or a salt. Although this powder is sufficiently effective, the thermoplastic resin that is the matrix resin is usually in the form of beads or pellets, and if the powder is used as it is, there is a possibility of classification. The polymer is preferably obtained as a granular powder.

The granular powder can be produced by adding a solvent during the coagulation with an acid or a salt to form a granule, by using an acid or a salt to form a granule by coagulating under a slow condition, and at a high temperature. A spray drying method or the like may be used in which latex is sprayed in an air stream to be dried and granular particles are produced.

In the expandable resin composition of the present invention, the graft copolymer and the thermoplastic resin are melt-mixed in advance to form a pellet-shaped masterbatch, which is added to the matrix resin to improve the handling property and the dispersion of the graft copolymer. It is more preferable from the viewpoint of improving the property. As the thermoplastic resin premixed with the graft copolymer, a thermoplastic resin of the same kind as the matrix resin or another thermoplastic resin dispersed in the matrix resin is used. At this time, the content of the graft copolymer in the masterbatch is preferably 5 to 40% by mass.

As a method for producing a pellet-shaped masterbatch, an extrusion granulation method using an extruder, a roll pellet method for cutting a roll sheet to obtain cube-shaped pellets,
It is possible to use a method of pelletizing with a briquetting roll having pellet-shaped depressions.

The thermoplastic resin used as the matrix resin in the present invention is not particularly limited, and polyethylene,
Polyolefin resin such as polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, etc., polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate, polycyclohexane terephthalate, polybutylene terephthalate (PBT), polybutylene naphthalate , Polycarbonate (P
C), a butadiene rubber graft copolymer (eg ABS
Resin), acrylic rubber graft copolymer, silicone-
Acrylic composite rubber copolymer, ethylene popylene rubber graft copolymer, high impact polystyrene (HIPS),
Styrene resin such as AS resin, vinyl chloride resin, polyacetal resin, polyphenylene sulfide resin, polyphenylene ether resin (PPE), polyamide resin (PA) such as nylon 6, nylon 66, acrylic resin such as PMMA, PET / PBT, PC / PBT, PBT /
ABS, PC / ABS, PA / ABS, PPE / PB
T, PPE / HIPS, PPE / PA and the like can be mentioned, but polyolefin resin is particularly preferable. These resins may be used alone or in combination of two or more.

The polyolefin resin preferably used as the thermoplastic resin in the present invention will be described in more detail. This includes polypropylene, polyethylene, poly-1-butene, polyisobutylene, a random or block copolymer of propylene and ethylene and / or 1-butene in any ratio, and ethylene and propylene in any ratio and a diene component. Of 50% by mass or less of ethylene-propylene-diene terpolymer, polymethylpentene, ethylene or propylene and 50% by mass or less of vinyl acetate, (meth) acrylic acid alkyl ester, an ethylenic compound such as an aromatic vinyl compound Random, block or graft copolymers with monomers other than olefins having unsaturated bonds are included.

In the present invention, the compounding amount of the rubber-based graft copolymer in the resin composition for foam molding is 1 to 90% by mass, preferably 5 to 50% by mass. If the compounding amount of the rubber-based graft copolymer is less than 1% by mass, the non-slip effect is not observed in the foamed molded product, and if it is more than 90% by mass, it becomes difficult to obtain a good foamed molded product. Further, when the amount of the rubber-based graft copolymer added is less than 40% by mass, when the rubber-based graft copolymer simple substance is added to the resin composition for foam molding, the rubber-based graft copolymer is contained in the resin composition for foam molding. Therefore, uneven distribution of the rubber-based graft copolymer is prevented by adding a master batch in which the rubber-based graft copolymer is melt-mixed with the thermoplastic resin in advance to the resin composition for foam molding. The thermoplastic resin used in the masterbatch is preferably a thermoplastic resin used in foam molding or a thermoplastic resin dispersed in the thermoplastic resin for foam molding during foam molding, and the amount of the rubber-based graft copolymer in the masterbatch. Is preferably 5 to 40% by mass. When the thermoplastic resin used in the masterbatch is not dispersed in the thermoplastic resin for foam molding during foam molding, the dispersibility in the resin composition for foam molding of the masterbatch is poor, and as a result, the rubber-based graft copolymer. Is unevenly distributed.

As the foaming agent that can be used for foam-molding the resin composition for foam molding of the present invention, known foaming agents can be used. For example, azodicarbonamide (A
DCA), dinitropentamethylenetetramine (DP
T), oxybisbenzenesulfonyl hydrazide (OBSH), sodium hydrogencarbonate (baking soda), and other chemical-type blowing agents that generate gas due to chemical changes, air, carbon dioxide, nitrogen gas, water, petroleum ether, acetone, hexane, Physical type foaming agents such as benzene, propane, butane, pentane, methylene chloride, ethylene chloride and freon can be selected.

The amount of the foaming agent used varies depending on the type of the foaming agent and the desired expansion ratio, but for example, the density is 0.01 to
The amount of the foaming agent used to obtain a foam of about 0.6 g / cm ^{3 is} about 0.2 to 25 parts by mass (converted to butane) of the volatile foaming agent per 100 parts by mass of the resin, and 0 for the inorganic foaming agent. .About.1 to 15 parts by mass (calculated as carbon dioxide), and about 0.1 to 20 parts by mass for the thermal decomposition type foaming agent.

As a means for obtaining a sheet-like foam from the resin composition for foam molding of the present invention, a foamable resin obtained by melt-kneading a resin, a rubber-based graft copolymer and a foaming agent in an extruder is extruded. An annular die provided at the tip of the equipment is extruded into a low pressure area to form an annular foam pair, and then the annular foam is brought into contact with the periphery of an annular cooling device divided into at least two to cool or extrude. It can be obtained by extruding into a low pressure region from a T-type die provided at the machine tip to form a sheet-like foam, and then cooling this sheet-like foam with a roll.

If desired, additives such as stabilizers, lubricants and fungicides can be added to the resin composition for foam molding of the present invention. As a stabilizer, pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4]
-Hydroxyphenyl) propionate] and other phenolic stabilizers, tris (monononylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and other phosphorus stabilizers, and dilaurylthiodipropionate And other sulfur-based stabilizers.

Examples of the lubricant include pure hydrocarbons such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, and low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxyfatty acids; fatty acid amides and bis. Fatty acid amides such as fatty acid amides; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, ester alcohols such as fatty alcohol esters (ester waxes) of fatty acids; lauric acid, palmitic acid, Higher fatty acid metal salt such as sodium, calcium or magnesium salt of oleic acid or stearic acid, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol , Partial esters of polyglycerol and the like; polyalkyl (meth) polymer lubricant acrylate copolymer and the like.

Examples of the processing aid include polytetrafluoroethylene particles, a modifier containing polytetrafluoroethylene particles, and a polyalkyl (meth) acrylate high molecular weight copolymer.

Examples of the plasticizer include di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-secondary butyl phthalate, di-heptyl phthalate, C7.
To C9 (alphanol) phthalate, di-normal octyl phthalate, di-isooctyl phthalate, di-
3,5,5-trimethylhexyl phthalate, normal octyl normal decyl phthalate, isooctyl isodecyl phthalate, di-isodecyl phthalate, di-methoxyethyl phthalate, di-butoxyethyl phthalate, di-butyl phthalate, di-hexyl phthalate,
Phthalates such as bis (diethyl glycol monomethyl ether) phthalate, di-isobutyl adipate, di-2-ethylhexyl adipate, di-isooctyl adipate, normal octyl normal decyl adipate, isooctyl isodecyl adipate, di-isodecyl adipate, Adipate such as di-butoxyethyl adipate, di-3,5,5-trimethylhexyl adipate, di-normal butyl sebacate, di-
Sebacic acid esters such as secondary butyl sebacate, di-2-ethylhexyl sebacate, di-alphanol sebacate, di-cyclohexyl sebacate, di-secondary butyl azelate, di-2-ethylhexyl azelate, di- Azelaic acid esters such as isooctyl azelate, tri-2-ethylhexyl phosphate, tri-butoxyethyl phosphate, tri-cresyl phosphate, tri-orthocresyl phosphate,
Tri-metacresyl phosphate, tri-para-cresyl phosphate, phenyl dicresyl phosphate, xylenyl dicresyl phosphate, cresyl dixylenyl phosphate, and other phosphate esters, trimellitic acid ester, polyester-based polymer plasticizer, epoxy Soybean oil,
Epoxy plasticizers such as epoxidized linseed oil may be mentioned.

Examples of the filler include calcium carbonate, talc, glass fiber, carbon fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, magnesium hydroxide, aluminum hydroxide and the like. As a representative example. Among these, calcium carbonate and talc are preferable.

Examples of the crosslinking agent include phenolic crosslinking agents and organic peroxides, and examples of the phenolic crosslinking agent include 2,6-di-t-butyl-P-cresol and 2,4,6-tril. -T-butylphenol, n-octadecyl-3-bropionate, styrenated phenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,5-di-t-butyl-hydroquinone, cyclohexylphenol, Butylhydroxyanisole, 2,2'-methylene-bis (4-methyl-6-
t-butyl-phenol), 2,2'-methylene-bis (4-ethyl-6-t-butyl roof enol), 4,
4'-iso-propylidene bisphenol, 4,4'-
Butylidene-bis (3-methyl-6-t-butylphenol), 1,1-bis (4-hydroxy-phenyl)
Cyclohexane, 4,4'-methylene-bis (2,6-
Di-t-butyl-phenol), 2,6-bis (2'-
Hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methyl-phenol, 1,1,3-tris (2
-Methyl-4-hydroxy-5-t-butyl-phenyl) butane, 1,3,5-tri-methyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxy-
Benzyl) benzene, tetrakis [methylene-3 (3,3
5-di-t-butyl-4-hydroxy-phenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate,
4,4′-thiobis (3-methyl-6-t-butylphenol), tris [β-3,5-di-t-butyl-4-
Hydroxyphenyl) propionyl-oxyethyl]
Isocyanate, 2,2'-thiobis (4-methyl-6)
-T-butylphenol), as the organic peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl -2,5 di (t
-Butylperoxy) hexyne-3,1,3-bis (t
-Butylperoxyisopropyl) benzene, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4 -Dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t-butylcumyl peroxide and the like.

As the flame retardant, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, Tris (chloroethyl) phosphate,
Phosphoric ester compounds such as alkoxy-substituted bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, polyphosphate such as trioxybenzene triphosphate, tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, Bistribromophenoxyethane, ethylene bistetrabromoftileimide, tribromophenol, various halogenated epoxy oligomers obtained by reaction of halogenated bisphenol A with epihalohydrin, carbonate oligomers containing halogenated bisphenol A, halogenated polystyrene , Halogen-containing compounds such as chlorinated polyolefin and polyvinyl chloride, metal hydroxide , Metal oxides, sulfamic acid compounds, and the like as typical examples respectively. Examples of antistatic agents include amine-based, ammonium-based, sulfonic acid-based, polyoxyethylene-based, polyether-polyamide block-based and the like.

Examples of the antibacterial / antifungal agent include imidazole-based, thiazole-based, nitrile-based, haloalkyl-based, pyridine-based, and the like, and silver-based, zinc-based, copper-based, titanium-based, and other inorganic-based agents. Are exemplified. Of these,
It is preferable to use a silver-based material that is thermally stable and has high performance. As a silver-based antibacterial agent, zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, calcium silicate and the like porous structure is loaded with silver, silver ion, silver complex, silver compound Examples thereof include silver salts of fatty acids and silver salts of alkyl phosphates.

[0066]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In addition,
In the description, "part" means mass part and "%" means mass%.

Production Example 1 Production of Diene Rubber Graft Copolymer (A) In a pressure resistant autoclave, 150 parts of deionized water, 85 parts of 1,3 butadiene, 15 parts of styrene, 0.5 part of t-dodecyl mercaptan, 0.4 parts of diisopropylbenzene hydroperoxide, 1.5 parts of sodium pyrophosphate, 0.02 part of ferrous sulfate, 1.0 part of dextrose and 1.0 part of potassium oleate were charged and stirred at 50 ° C. The reaction was carried out for 15 hours to produce a butadiene rubber polymer latex.

65 parts (as solid content) of the obtained butadiene rubber polymer latex was charged into a flask, and after nitrogen substitution, 1.2 parts of NaHCO ₃ as a foaming agent was added as a 10% aqueous solution and stirred for 30 minutes. did. Next, 1 part of potassium oleate was added as a 7% aqueous solution and stabilized, and then 0.6 part of rongalite was added and the internal temperature was kept at 70 ° C. to prepare 35 parts of a monomer mixture having the following composition. Graft-polymerized. As a first stage of grafting, 40 parts of methyl methacrylate, 5 parts of ethyl acrylate and 0.1 part of t-butyl hydroperoxide (hereinafter abbreviated as t-BH) are used as 100 parts of the total graft monomer mixture. 1 body mixture
The mixture was added dropwise over a period of time and polymerized for 2 hours while stirring. After that, 40 parts of styrene and t-BH were used as the second stage of grafting.
0.1 part of the mixture was added dropwise over 1 hour and polymerized for 2 hours while stirring. Further, as a third stage of grafting, a monomer mixture of 15 parts of methyl methacrylate and 0.05 part of t-BH was added dropwise over 1 hour and polymerized for 2 hours while stirring to diene rubber graft copolymer (A) latex. Got

After adding 0.5 part of t-BH to the obtained graft copolymer (A) latex, 0.2% aqueous sulfuric acid solution was added to cause coagulation and solidified by heat treatment at 90 ° C. Then, the coagulated product was washed with warm water and further dried to obtain a diene rubber graft copolymer (A) powder.

Production Example 2 Production of Acrylic Rubber Graft Copolymer (B) To a separable flask equipped with a stirrer, 195 parts of distilled water and 0.1 part of sodium dodecylbenzenesulfonate were added, and the atmosphere was replaced with nitrogen. To 50 ° C., and then a mixed solution of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit and 5 parts of distilled water was charged, and the atmosphere was replaced with nitrogen. A mixture of 70 parts of butyl acrylate, 0.75 part of allyl methacrylate and 0.4 part of t-BH was charged to initiate radical polymerization, and then the internal temperature was maintained at 70 ° C. for 2 hours to complete the polymerization. A latex was obtained. A part of this latex was sampled and the average particle size was measured to be 0.22.
was μm.

A mixed solution of 0.06 part of t-BH and 30 parts of methyl methacrylate was added dropwise to this rubber latex at 70 ° C. for 15 minutes and then kept at 70 ° C. for 4 hours to complete the graft polymerization on the rubber. An acrylic rubber-based graft copolymer (B) latex was obtained. The polymerization rate of methyl methacrylate is 98.2%, and the average particle size is 0.24.
was μm. The obtained graft copolymer (B) latex was dropped into 200 parts of hot water containing 1.5% of calcium chloride, coagulated, separated, washed, and then dried at 75 ° C. for 16 hours,
An acrylic graft copolymer (B) powder was obtained.

Production Example 3 Production of Silicone / Acrylic Rubber Graft Copolymer (C) 2 parts tetraethoxysilane, 0.5 part γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts octamethylcyclotetrasiloxane. Were mixed to obtain 100 parts of a siloxane mixture. To 200 parts of distilled water in which 0.67 parts of sodium dodecylbenzenesulfonate and 0.67 parts of dodecylbenzenesulfonic acid were dissolved, 100 parts of the above-mentioned mixed siloxane was added, and the mixture was mixed with a homomixer for 10,000 times.
After pre-stirring at 0 rpm, use a homogenizer to
It was emulsified and dispersed at a pressure of 9.6 Pa to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C for 5 hours with mixing and stirring, and then allowed to stand at 20 ° C, and after 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution.
Was neutralized to 7.0 to complete the polymerization, and polyorganosiloxane latex (hereinafter referred to as PDMS-1
Called. ) Got. The polymerization rate of the obtained PDMS-1 was 89.1%, and the average particle diameter of PDMS-1 was 0.1.
It was 9 μm. Also, this PDMS-1 was coagulated and dried with isopropanol to obtain a solid, which was dried with toluene at 90 ° C., 1
It was extracted for 2 hours and the gel content was measured and found to be 91.4%.

35 parts of the obtained PDMS-1 was taken and put in a separable flask equipped with a stirrer, and distilled water 175
Part, and after nitrogen substitution, the temperature was raised to 50 ° C., and a mixed solution of 78.4 parts of n-butyl acrylate, 1.6 parts of allyl methacrylate and 0.3 part of t-BH was charged and stirred for 30 minutes. The mixture was infiltrated into the polyorganosiloxane particles. Then, a mixed solution of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.3 parts of Rongalit and 10 parts of distilled water was charged to start radical polymerization, and then the internal temperature was 70 ° C. for 2 Holding for a while to complete the polymerization, a composite rubber latex was obtained. A part of this latex was collected and the average particle size of the composite rubber was measured and found to be 0.22 μm. Further, this latex is dried to obtain a solid matter, which is extracted with toluene at 90 ° C. for 4 hours,
The gel content was measured and found to be 95%.

6 parts of a mixed solution of 10 parts of methyl methacrylate and 0.024 part of t-BH was added to the composite rubber latex.
The mixture was added dropwise at 0 ° C. for 15 minutes and then kept at 60 ° C. for 2 hours to complete graft polymerization on the composite rubber. The polymerization rate of methyl methacrylate was 97.1%. The average particle size of the graft copolymer latex is 0.23 μm
Met. The obtained graft copolymer latex was added to 40
At 5 ℃, the ratio of 5% calcium chloride solution is 1: 2
Then, the temperature was raised to 90 ° C. to coagulate, and the solid content was separated after repeated washing with water.
It was dried at ℃ for 24 hours to obtain a polyorganosiloxane-based graft polymer (C) powder.

Production Example 4 Production of Rubber-Based Graft Copolymer Masterbatch The rubber-based graft copolymer (A) obtained in each of the above Production Examples,
(B) and (C) 20 parts each and a mixture of 80 parts of polypropylene resin or 80 parts of polyethylene resin are supplied to an extruder. The polypropylene resin is melt-kneaded at 190 ° C and the polyethylene resin at 160 ° C, and extruded from a die nozzle. The obtained product was cut to obtain a pellet-shaped rubber-based graft copolymer masterbatch.

The rubber-based graft copolymer (A),
A master batch of (B) and (C) made of polypropylene resin is A-1, B-1, C, and a master batch of polyethylene resin is A-2,
It was set to B-2 and A. The polypropylene resin and polyethylene resin used are as follows. The melt flow rate (MFR) was measured according to ASTM D1238. Polypropylene resin: Nippon Polychem Co., Ltd. FY-4
(MFR = 5 g / 10 min) Low density polyethylene: LFI1 manufactured by Nippon Polychem Co., Ltd.
22 (MFR = 0.3g / 10min)

[Examples 1 to 3], [Comparative Example 1] Production Example 4
The rubber-based graft copolymer masterbatch A-1 obtained in
25 parts of each of B-1 and C, 75 parts of the following polypropylene resin mixed with 7.5 parts of the following foaming agent, or 100 parts of polypropylene resin mixed with 7.5 parts of the following foaming agent (Comparative Example 1 ) Is supplied to each extruder at a temperature of 230
Width 20c, which was melt-kneaded at ℃ and installed at the tip of the mouth of the extruder
It was extruded from a flat die of m to obtain a foamed sheet having a thickness of 1 mm. The expansion ratio of these obtained foamed resin sheets was 3 times. Polypropylene resin: Nippon Polychem Co., Ltd. FY-4
(MFR = 5 g / 10 min) Foaming agent: Mitsubishi Chemical Co., Ltd. FineBlow S20 (baking soda-based foaming agent, trade name) Extruder: IKG Co., Ltd. MS50-28

[Examples 4 to 6], [Comparative Example 2] Production Example 4
The rubber-based graft copolymer masterbatch A-2 obtained in
20 parts of B-2 and A respectively, the following polyethylene resin 8
A mixture of 0 parts or the polyethylene resin (Comparative Example 2) was supplied to an extruder, 9% of isobutane as a foaming agent was pressed into the resin inside the extruder, and the mixture was melt-kneaded at 160 ° C. It was extruded from an annular lip of a circular die attached to the tip of the mouth to obtain a foamed sheet having a thickness of 2 mm. The expansion ratio of these foamed resin sheets was 20 times. Low density polyethylene: LFI1 manufactured by Nippon Polychem Co., Ltd.
22 (MFR = 0.3 g / 10 min) Extruder: VSK50 manufactured by Nakatani Machinery Co., Ltd.

The foamed sheets obtained in the above Examples and Comparative Examples were tested for dynamic friction coefficient. The results are collectively shown in Tables 1 and 2. As is clear from the table, it was confirmed that the foamed sheet to which the rubber-based graft copolymer was added had a higher dynamic friction coefficient and improved non-slip properties than the foamed sheet to which the rubber-based graft copolymer was not added. The "dynamic friction coefficient" test was performed using a friction tester manufactured by Toyo Seiki Seisakusho according to JISK712.
It carried out based on 5.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

The non-slip foamed resin molded product foam-molded from the resin composition for foam molding of the present invention is excellent in fitability derived from non-slip, and is used as a floor covering for a silent floor in the field of construction. Alternatively, it is suitable as a soundproofing / heat insulating material, in the packaging field as a cushioning material for preventing damage to transportation articles, and further as an interior material for vehicles such as automobiles. According to the present invention, no special processing conventionally required for a non-slip foam-molded article is required, and its application can be greatly expanded, and its industrial utility value is great.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masao Mohri             3816 Noborito, Tama-ku, Kawasaki-shi, Kanagawa Mitsubishi             Rayon Co., Ltd. Tokyo Technology and Information Center             Within (72) Inventor Masahiro Osuka             3816 Noborito, Tama-ku, Kawasaki-shi, Kanagawa Mitsubishi             Rayon Co., Ltd. Tokyo Technology and Information Center             Within F-term (reference) 4F070 AA06 AA13 AA15 AA16 AA22                       AA32 AA42 AA47 AA50 AA52                       AA54 AA59 AB08 AB09 FA03                       FB03                 4F074 AA08D AA17 AA22 AA24                       AA25 AA32 AA35 AA48D                       AA57 AA66 AA70 AA90D                       BA03 BA06 BA13 BA32 BA33                       BA34 BA45 BA74 BA75 DA33                       DA35 DA58                 4J002 BB031 BB061 BB121 BB151                       BC061 BD041 BN122 BN142                       BN172 CB001 CF051 CF061                       CF071 CG011 CH071 CL011                       CL031 CN011 FD320 GL00                       GN00

Claims (5)

[Claims] 1. A resin composition for foam molding, comprising at least a rubber-like polymer, a graft copolymer obtained by graft-polymerizing at least one vinyl-type monomer copolymerizable therewith, and a thermoplastic resin. . 2. A pellet-shaped masterbatch in which the graft copolymer and the thermoplastic resin according to claim 1 or a thermoplastic resin of the same kind as the thermoplastic resin or another thermoplastic resin dispersed in the thermoplastic resin are melt-mixed in advance. The resin composition for foam molding according to claim 1, wherein the resin composition is added to the thermoplastic resin. 3. A resin composition obtained by foam-molding a rubber polymer, to which a graft copolymer obtained by graft-polymerizing at least one vinyl monomer copolymerizable with the rubber polymer is added to a thermoplastic resin. Non-slip foamed resin molded product. 4. The non-slip foamed resin molded article according to claim 3, wherein the foamed resin molded article is in the form of a sheet. 5. The non-slip foamed resin molded article according to claim 3 or 4, wherein the thermoplastic resin is a polyolefin resin.