JP2016191022A - Foaming resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foaming resin molding having no stickiness, and having continuous water repellency and rubbing noise prevention performance.SOLUTION: A foaming resin molding is obtained by foaming and molding a resin composition comprising the following components (A)-(C): (A) a thermoplastic resin; (B) a polyorganosiloxane modified polypropylene obtained by the chemical bonding between (b1) a polypropylene resin and (b2) a polyorganosiloxane comprising at least one silicon atom-bonding radical-polymerizable functional group in one molecule; and (C) a foaming agent.SELECTED DRAWING: None

Description

  The present invention relates to a foamed resin molded article having no stickiness and having continuous water repellency and anti-friction properties.

  Foamed resin moldings are widely used in automobile interior materials, electrical insulation members for electrical appliances, containers, food trays, thermal insulation foam construction materials, sealing materials, and the like. However, it has been pointed out that foamed resin moldings have insufficient water repellency and rubbing noise prevention.

  A conventional technique for improving the above-mentioned problems of the foamed resin molded article is a seal characterized by applying a specific modified dimethylpolysiloxane to at least a part of the surface of the open-cell foamed polyolefin resin. Material (Patent Document 1), a fine ripple pattern is formed on the surface of a polyethylene resin foam sheet, the glossiness of at least one surface is 10 or less, and the contact angle of water is 85 degrees or more Foamed resin molding comprising a polyethylene resin foam sheet (Patent Document 2), a wax having a melting point of 40 to 100 ° C., and an emulsion in which a mineral oil having a pour point of −10 ° C. or less is dispersed in an aqueous dispersion medium. A rubbing sound-suppressing foamed resin molded article (Patent Document 3) characterized by being applied to the surface of a body is disclosed.

  However, the method of Patent Document 1 has a problem in the continuity of the water repellent effect because the applied specific modified polydimethylsiloxane is missing. In the method of Patent Document 2, the uneven portion having a fine ripple pattern is buried during use and the water repellent effect is lost, which also has a problem in the continuity of the water repellent effect. In the method of Patent Document 3, since the applied wax is lost by rubbing against other members, there is a problem in the continuity of the effect of preventing rubbing noise. For this reason, there has been a demand for a foamed resin molded article having excellent water repellency and anti-friction property with excellent continuity.

Japanese Patent Laid-Open No. 3-149235 JP 2010-121024 JP 2011-231256 A

  An object of the present invention is to provide a foamed resin molded article having no stickiness and having continuous water repellency and anti-friction properties.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by producing a foamed resin molded article containing polyorganosiloxane-modified polypropylene as a surface modifier. . The present inventor has further studied based on these findings and has completed the present invention.
That is, the present invention has the following configuration.
[1] A foamed resin molded article obtained by foam-molding a resin composition containing the following components (A) to (C).
(A) Thermoplastic resin (B) (b1) Polypropylene resin and (b2) A polyorganosiloxane containing at least one silicon atom-bonded radically polymerizable functional group in one molecule is chemically bonded. The organosiloxane-modified polypropylene (C) foaming agent [2] The polyorganosiloxane-modified polypropylene of (B) further contains (b3) a non-radically polymerizable polyorganosiloxane, as described in [1] above Foamed resin molding.
[3] The polyorganosiloxane-modified polypropylene of (B) is a polyorganosiloxane-modified polypropylene further containing (b4) polypropylene wax and (b2) chemically bonded to (b1) and (b4). The foamed resin molded article according to the above [1] or [2], wherein

  The foamed resin molded article of the present invention has no stickiness on the surface, and has continuous water repellency and anti-friction properties.

  (A) A thermoplastic resin (hereinafter also referred to as “component A”) is a resin constituting a foamed resin molded body. Examples of the thermoplastic resin include olefin resins; styrene resins; polyamide resins such as 6-nylon, 66-nylon, and 12-nylon; polyamide imides; polyurethanes; polyimides; polyether imides; Polyvinyl chloride; Polyvinyl fluoride; Alkenyl aromatic resin; Polyester resin such as polyethylene terephthalate and polybutylene terephthalate; Polycarbonate such as bisphenol A polycarbonate; Polyacetal; Polyphenylene sulfide. One or more of these thermoplastic resins may be used, but olefin resins, styrene resins and the like are widely used in terms of price and performance.

  Examples of the olefin resins include polypropylene, block copolymers of propylene and ethylene, α-olefins other than propylene such as butene-1, random copolymers, high density polyethylene, low density polyethylene, linear low density polyethylene, Block copolymer, random copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meta) of ethylene and ethylene such as butene-1 and α-olefins other than propylene ) Acrylic acid ester copolymer, poly-4-methyl-pentene-1, etc. may be mentioned, and these may be used alone or in combination of two or more.

  Examples of the styrene resin include polystyrene (GPPS), high impact polystyrene (HIPS), styrene-acrylonitrile copolymer (AS), styrene-acrylic acid copolymer (SAc), and styrene-methacrylic acid copolymer (SMAc). , Styrene-methyl methacrylate copolymer (MS), styrene-maleic anhydride copolymer (SMAH), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-propylene-nonconjugated diene-styrene copolymer Examples thereof include a combination (AES) and a methyl methacrylate-butadiene-styrene copolymer (MBS), and these may be used alone or in combination of two or more. Among these, GPPS and HIPS are preferable from the viewpoints of processability and economy.

  The polyorganosiloxane-modified polypropylene (B) (hereinafter also referred to as “component B”) contains (b1) a polypropylene resin and (b2) at least one silicon-bonded radically polymerizable functional group in one molecule. A polyorganosiloxane is chemically bonded (grafted). The B component is used as a surface modifier, and exhibits effects such as water repellency, slidability, and anti-friction property by the polyorganosiloxane chain contained in the B component, and continuity of the above effect by the polypropylene chain. To do.

  (B1) Polypropylene resin (hereinafter also referred to as “b1 component”) constituting component B is a propylene homopolymer, or a block copolymer of propylene and an α-olefin other than propylene such as ethylene and butene-1. , A resin such as a random copolymer, a copolymer such as a graft copolymer, and a mixture thereof.

  The skeleton of polyorganosiloxane (hereinafter also referred to as “b2 component”) containing at least one silicon atom-bonded radically polymerizable functional group in one molecule constituting the component B (b2) is linear or branched. May be cyclic, or a mixture thereof. Examples of polyorganosiloxanes include dimethylvinylsiloxy group-blocked polydimethylsiloxane at both ends, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylsiloxane copolymer at both ends, trimethylsiloxy group-blocked polymethylvinylsiloxane at both ends, and trimethylsiloxy at both ends. Group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both ends dimethylhexenylsiloxy group-blocked polydimethylsiloxane, both ends dimethylhexenylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer, both ends trimethylsiloxy group-blocked polymethylhexenylsiloxane And dimethylsiloxane / methylhexenyl copolymer blocked with trimethylsiloxy groups at both terminals.

  The radical polymerizable functional group is an organic group having a carbon-carbon double bond and capable of radical polymerization. For example, an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacrylic group. Roxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- ( 3-vinylphenyl) ethyl group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, decenyl group and the like. Of these, a vinyl group is most preferred from the viewpoint of synthesis and availability.

  Examples of organic groups other than radical polymerizable functional groups include methyl groups, ethyl groups, propyl groups, alkyl groups such as 3,3,3-trifluoropropyl groups, and 3-chloropropyl groups, cyclopentyl groups, and cyclohexyl groups such as cyclohexyl groups. Examples thereof include aryl groups such as alkyl groups, phenyl groups, and xylyl groups, aralkyl groups such as benzyl groups, phenethyl groups, and 3-phenylpropyl groups, alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups, and hydroxy groups.

  The b2 component has various kinematic viscosities, and any of them can be used. Preferably, the k2 has a kinematic viscosity of about 200 to 1,000,000 mm 2 / s at 25 ° C., more preferably about 500. ~ 1 million mm2 / s. If a material other than the kinematic viscosity in the above range is used, the effects of the present invention may be difficult to be achieved, and it may be difficult to be suitable in terms of processing the surface modifier that is the B component.

  The B component is obtained by heating and kneading a mixture containing the b1 component and the b2 component in the presence or absence of an organic peroxide and chemically bonding the b1 component and the b2 component. A preferred method for obtaining the B component is a method in which the b1 component and the b2 component are heated and kneaded in the presence of an organic peroxide and chemically bonded in order to perform chemical bonding in a short time.

  The organic peroxide generates radicals by heating, and promotes chemical bonding between the b1 component and the b2 component in a short time. Specifically, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as isobutyryl peroxide, lauroyl peroxide, and benzoyl peroxide, and hydroperoxides such as diisopropylbenzene hydroperoxide Oxide, dicumyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 1,3-bis- (t-butylperoxy-isopropyl) -benzene, di-t- Dialkyl peroxides such as butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane-3, 1,1-di-t-butylperoxy-3,3,5 -Trimethylcyclo Peroxyketals such as xane, 2,2-di- (t-butylperoxy) -butane, alkyl peresters such as t-butylperoxy-pivalate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate And the like.

  As the organic peroxide, commercially available ones can be used, and examples thereof include Luperox 101, Luperlock Sulpelox DC, Luperlox F, Luperlox DI (all trade names; manufactured by Arkema Yoshitomi).

  As the B component, a component obtained by further blending (b3) non-radically polymerizable polyorganosiloxane (hereinafter also referred to as “b3 component”) with the b1 component and the b2 component can be used. A foamed resin molded article using such a component B is also one form of the present invention.

  The b3 component is a polyorganosiloxane different from the b2 component, and does not contain a radical polymerizable functional group that binds to a silicon atom, which is an essential component of the b2 component. Therefore, the b3 component is not chemically bonded to the b1 component.

  The skeleton of the non-radically polymerizable polyorganosiloxane may be linear, branched or cyclic, or a mixture thereof. Examples of the non-radically polymerizable polyorganosiloxane include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, higher fatty acid-modified polydimethylsiloxane, Fluorine modified polydimethylsiloxane, amino modified polydimethylsiloxane, epoxy modified polydimethylsiloxane, carbinol modified polydimethylsiloxane, carboxyl modified polydimethylsiloxane, phenol modified polydimethylsiloxane, silanol modified polydimethylsiloxane, aralkyl modified polydimethylsiloxane, alkyl Examples thereof include modified polydimethylsiloxane.

  There is no restriction | limiting in particular about the mixing | blending time of b3 component, Any may be before heating kneading, during heating kneading, and after heating kneading. When adding after heat-kneading, it is preferable to heat-knead so that b3 component may become uniform with the coupling body (graft body) which grafted b1 component and b2 component. Although b3 component does not graft with b1 component and forms a graft body, continuous water repellency is exhibited more by using it by the structure of this invention.

  The B component contains the b1 component and the b2 component, or the b1 component, the b2 component, and the b3 component, and (b4) polypropylene wax (hereinafter also referred to as “b4 component”), and the b2 component includes the b1 component and the b4 component. Those containing chemical bonds can be used. A foamed resin molded article using such a component B is also one form of the present invention.

  The component b4 is obtained by polymerizing propylene or depolymerizing a general high molecular weight polypropylene. The number average molecular weight of the polypropylene wax is preferably a low molecular weight polypropylene of about 1000 to 20000.

  As the b4 component, commercially available products can be used. For example, Biscol 330-P, Biscol 440-P, Biscol 550-P, Biscol 660-P (all trade names: Sanyo Chemical Industries, Ltd.), Hi Examples thereof include wax NP055, high wax NP105, high wax NP505, high wax NP805 (all trade names; manufactured by Mitsui Chemicals), lycowax PP230 (trade names; manufactured by Clariant).

  By using the b4 component in combination, it is possible to obtain the B component with less aggregate (aggregate obtained by polymerizing the b2 component). The cause of this is not clear, but it is thought that the presence of the b4 component lowers the melt viscosity of the b1 component and improves the compatibility between the b1 component and the b2 component. By using the B component with less aggregates in the foamed resin molded article of the present invention, in addition to the effects of the present invention, there is an effect that a foamed resin molded article having a clean appearance without aggregates on the surface can be obtained.

  The B component used in combination with the b4 component as described above includes those in which the b2 component is chemically bonded to the b1 component and the b4 component. In addition, the b2 component and the b1 component are chemically bonded, and the b2 component and the b4 component. The component may include chemically bonded components.

  In the B component, a known kneader can be used as a method for heating and kneading the above b1 component and b2 component, or b1 component and b2 component, and further b3 component and / or b4 component, for example, a Banbury mixer, a kneader, A single screw extruder, a twin screw extruder, etc. can be used. Among these, a twin screw extruder is preferable when considering productivity, kneading force, and the like. The twin-screw extruder includes two-axis different-direction rotation non-meshing type extruder, two-axis different-direction rotation non-meshing type extruder, two-axis same-direction rotation non-meshing type extruder, two-axis same-direction rotation meshing type There are extruders, and any of them can be used. However, in order to increase the dispersibility of each component and suppress the progress of local reaction, it is preferable to use a biaxial co-rotating meshing extruder.

  The heating temperature at the time of kneading may be a temperature that is not lower than the temperature at which the b1 component melts and does not deteriorate the resin too much, and specifically, for example, is in the range of 120 to 250 ° C. . The time for heating and kneading varies depending on the kneading machine to be used, heating conditions, and the like. For example, when a twin screw extruder is used as the kneading machine, it is preferably about 30 seconds to 10 minutes, more preferably 1 to 5 minutes.

  The blending amount of the b2 component contained in the B component is preferably about 0.5 to 200 parts by weight, more preferably about 2 to 150 parts by weight with respect to 100 parts by weight of the b1 component or the b1 and b4 components. Parts, more preferably about 10 to 100 parts by weight. When the blending amount of the b2 component is out of the above range, it may be difficult to obtain the effect of the present invention.

  When an organic peroxide is used as the B component, the amount of the organic peroxide is preferably about 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the b1 component or the b1 and b4 components. More preferably, it is about 0.05 to 3.0 parts by mass. Within the above range, the b2 component and the b1 component, or the b2 component, the b1 component, and the b4 component can be grafted smoothly, which is preferable.

  When the b3 component is used as the B component, the blending amount of the b3 component is preferably about 5 to 50 parts by mass with respect to 100 parts by mass of the b1 component and the b2 component, or the b1, b2, and b4 components. More preferably, it is about 10-30 mass parts. Within the above range, continuous water repellency is more exhibited, which is preferable.

  When the b4 component is used as the B component, the blending ratio (mass ratio) of the b1 component: b4 component is preferably about 99: 1 to 40:60, more preferably about 90: 10 to 45:55, more preferably about 80:20 to 50:50. Within this range, B component with few aggregates can be obtained, which is preferable.

  The B component used in the present invention may be blended with various additives that are usually added to polypropylene resins within a range not inhibiting the present invention. For example, surface modifiers (water repellents, lubricants, release agents, etc.) other than component B (surface modifiers), thermal stabilizers, antioxidants, fillers, colorants, antistatic agents, antifogging agents, You may mix | blend various additives, such as a neutralizer, a weather resistance agent, a ultraviolet absorber, a flame retardant, an antiblocking agent, and an impact modifier.

  As a compounding quantity of B component in a foamed resin molding, it is about 0.1-20 mass parts with respect to 100 mass parts of A component, More preferably, it is about 1-5 mass parts.

  (C) The foaming agent (hereinafter also referred to as “C” component) is not particularly limited as long as it is a known foaming agent that foams the resin (component A) constituting the foamed resin molded body. For example, a physical foaming agent, Examples include chemical foaming agents.

Examples of the physical foaming agent include hydrocarbon-based propane, butane, pentane, their normal structure or iso structure, and mixtures thereof, ethers such as dimethyl ether, carbon dioxide, nitrogen, alcohol , Water and the like.
Although there is no restriction | limiting in particular as a form of a physical foaming agent, For example, forms, such as a supercritical fluid and a thermally expansible microcapsule, can be illustrated. Supercritical fluids include those in which a physical foaming agent such as nitrogen or carbon dioxide is brought into a supercritical state. When a physical foaming agent in a supercritical fluid state is injected into a resin composition, the injection amount is accurate. There is an advantage that a large amount of physical foaming agent can be dissolved in the resin composition because of its high pressure and controllability. Examples of the heat-expandable microcapsules include those in which a hydrocarbon that is a physical foaming agent is included in a microcapsule of a thermoplastic resin, and when the microcapsule becomes high temperature, the outer shell of the microcapsule is softened and included. The hydrocarbons are vaporized to generate bubbles.

  Examples of the chemical foaming agent include organic chemical foaming agents such as azodicarboxylic acid amide, dinitropentamethylenetetramine, and 4,4oxybis (benzenesulfonylhydrazine), and inorganic chemicals such as sodium bicarbonate, citric acid, and ammonium carbonate. Examples include foaming agents.

  The blending amount of component C with respect to the resin (component A) constituting the foamed resin molded body is appropriately set depending on the foaming ratio of the desired foamed resin molded body, the type of foaming agent, the resin temperature during molding, and the foam molding method. That's fine. For example, usually, in the case of an inorganic chemical foaming agent, the amount is preferably about 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component A.

The foamed resin molded article of the present invention may use a crosslinking agent, a crosslinking aid and the like in order to increase the strength.
The crosslinking agent is preferably a radical generator such as an organic peroxide or the like, such as dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, cumene hydroperoxide, Cite 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and t-butylhydroperoxide Preferably, 2,5-dimethyl-2,5-di (t-butyl peroxide) hexane or the like is used.

  The crosslinking aid is an agent for efficiently performing the crosslinking reaction, and is an essential agent for crosslinking polypropylene, which is a degradable resin. For example, divinylbenzene, diallylbenzene, divinylnaphthalene, divinylbiphenyl, divinylcarbazole, divinylpyridine, and their nuclear-substituted compounds and homologues, ethylene glycol di (meth) acrylate, diallyl phthalate, triallyl formal, triallyl cyanurate, Multifunctional monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Examples include silane compounds such as trimethoxysilane and mixtures of two or more thereof.

  The foamed resin molded article of the present invention includes, for example, an air conditioner, a flame retardant, a lubricant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, a pigment, and a dye as long as the effects of the present invention are not impaired. Various additives and plasticizers such as mineral oil may be blended.

The foamed resin molded article of the present invention can be obtained by foaming and molding a resin composition containing an A component, a B component and a C component by a known method.
The order of blending the A component, B component and C component and the blending method are not particularly limited. For example, the A component and the B component are raw materials using a kneader such as a single screw extruder, twin screw extruder, Banbury mixer, etc. After melt-kneading, a method of foaming and molding with a known method using the C component, a method of dry blending the A component and the B component and then foaming and molding with a known method using the C component, etc. Can be mentioned.

  The foaming method for obtaining the foamed resin molded body is not particularly limited, and foaming can be performed by a known foaming method. Examples thereof include an extrusion foaming method, an injection foaming method, a bead foaming method, and a press foaming method. .

As a method of producing a foamed resin molded body by foaming by extrusion foaming method, for example, when using a single screw extruder, after A component, B component and C component are dry blended, they are put into an extruder and foamed. Then, a method of extruding an extruded foam from a die to obtain a foamed resin molded body can be mentioned. In addition, when using a connection type extruder, the A component and the B component are heated and kneaded by a first stage extruder to obtain a molten resin, and further, the foaming gas generated by adding the C component is kneaded, Examples include a method of cooling with an extruder in the second and subsequent stages and then extruding an extruded foam from a die to obtain a foamed resin molded body. The die may be appropriately selected from a circular type or a slit type as long as a desired product is obtained.
Furthermore, if necessary, it may be processed into an arbitrary shape by a known secondary forming method such as a vacuum / pressure forming method, a vacuum forming method, a plug forming method, a press forming method, or a double-sided vacuum forming method.

As a method for producing a foamed resin molded body by foaming by an injection foaming method, for example, after dry blending C component of chemical foaming agent or physical foaming agent (foamable microcapsule, etc.), A component and B component And a method of obtaining a foamed resin molding by injection into a mold using an injection molding machine. In addition, instead of using a chemical foaming agent, a method of injecting a physical foaming agent from an injection port of a barrel of an injection molding machine and injecting it into a mold using the injection molding machine to obtain a foamed resin molded body may be mentioned.
As a method for foaming the resin injected into the mold, a known method such as a short shot method, a full shot method, or a core back method can be used.

  As a method for producing the foamed resin molded body of the present invention by a bead foaming method, for example, in the case of a polypropylene resin foam, a resin composition containing a polypropylene resin (component A) containing no foaming agent and a component B is used as an extruder. The pellets and the low boiling point volatile blowing agent (component C) are treated in a high temperature and high pressure tank to obtain impregnated beads. The obtained impregnated beads are heated with water vapor, preliminarily foamed to adjust the particle diameter of the foamed cells, and further transferred to an aging step for returning the internal pressure of the beads to normal pressure, and sufficiently brought into contact with air. Further, this aged bead is heated with steam or the like in a mold to form a foam, and a foamed resin molded body can be produced by performing a known molding method.

  Although there is no restriction | limiting in particular as a use of the foamed resin molding of this invention, For example, a food container, a motor vehicle material, household appliance material, OA equipment machine material, building materials, drainage equipment, toiletry material, various tanks, containers, a sheet etc. are mentioned. It is done. Examples of food containers include trays, cups, dishes, and bowls. Automotive materials include interior parts such as door trims, pillars, instrumental panels, consoles, rocker panels, armrests, door inner panels, spare tire covers, trunk mats, bumpers, spoilers, fenders, side steps, doors and outers. Examples include exterior parts such as panels, other parts such as air intake ducts, coolant reserve tanks, radiator reserve tanks, window washer tanks, fender liners and fans, and integrally molded parts such as front and end panels. Home appliance materials include, for example, washing machine materials (outer tub, inner tub, lid, pulsator, balancer, washing pan, etc.), dryer materials (exterior, inner box, lid, etc.), vacuum cleaner materials, rice cookers Examples include materials, pot materials, heat insulator materials, dishwasher materials, air cleaner materials, and the like. Examples of OA equipment / media-related materials include cases of magnetic recording media and optical recording media, packaging sheets, parts for personal computers, parts for printers, and the like. Examples of the building material include a frame that hardens concrete, a wall member, and the like. Examples of drainage facilities include pipes and pump parts. Examples of container materials include food filling containers, transport containers, and costume containers. Moreover, the pallet for transportation etc. are mentioned.

  The present invention will now be described by way of examples, which are merely illustrative of the invention and do not limit the invention.

<Preparation of component B (polyorganosiloxane-modified polypropylene: surface modifier)>
(1) Raw material [component b1]: Polypropylene resin b1-1: Prime Polypro J-105G (trade name; manufactured by Prime Polymer, Homo PP, MI = 9)
b1-2: Wintech WFX4T (trade name; manufactured by Nippon Polypro Co., Ltd., metallocene random PP, MI = 7)
[Component b2]: Polyorganosiloxane b2 containing at least one silicon atom-bonded alkenyl group in one molecule: XF40A-1987 (trade name; manufactured by Momentive Performance Materials Japan, kinematic viscosity 1500 mm ² / s )
[Organic peroxide]
Organic peroxide (trade name: Luperox 101; manufactured by Arkema Yoshitomi, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane)
[Component b3]: Non-radically polymerizable polyorganosiloxane b3: TSF451-50 (trade name; manufactured by Momentive Performance Materials Japan, kinematic viscosity 50 mm ² / s)
[Component b4]: Polypropylene wax b4: Biscol 330-P (trade name; manufactured by Sanyo Chemical Industries, Ltd., molecular weight 15,000)

(2) Blending of component B (surface modifier) Tables 1 and 2 show the blending of component B produced using the above raw materials.

(3) Preparation of B component (surface modifier) [Preparation of B-1 to B-3, B-6]
10 times the amount of raw material of the composition shown in Table 1 using a twin-screw co-rotating meshing extruder (model: model: MFU15TW-45MG-NH; manufactured by Technobel, screw diameter = 15 mm, L / D = 45) Then, B component (B-1 to B-3, B-6) was prepared by the following method.
That is, the barrel (C1 to C6, H / D) temperature is set to 80 to 200 ° C. (C1 = 80 ° C., C2 = 160 ° C., C3 to C6 = 200 ° C., H / D = 200 ° C.), and the screw rotation speed is 600 rpm. The raw materials other than the b2 component and the b3 component are added from the raw material charging port of the two-shaft, same-direction rotary meshing extruder, and the b2 component and the b3 component are added from the C2 barrel using a liquid addition apparatus, and the B component (B -1 to B-3, B-6).

[Production of B-4]
B-3 obtained by heating and kneading the B-3 obtained by the same method as the preparation of the B component and 10 times the amount of the b3 component shown in Table 1 by the following method was prepared.
That is, the barrel (C1 to C6, H / D) temperature is 180 to 200 ° C. (C1 = 180 ° C., C2 to C6 = 200 ° C., H / D = 200 ° C.) and the screw rotation speed is 300 rpm. B-3 produced from the raw material inlet of the rotary meshing extruder was added, and the b3 component was added from the C2 barrel using a liquid addition device to produce B component (B-4).

[Production of B-5]
In preparation of B-4, B component (B-5) was prepared in the same manner except that B-1 was used instead of B-3.

Here, the degree (graft rate) in which the b2 component added to the B component was chemically bonded (grafted) to the b1 component and the b4 component was measured by the following method.
About 1 g of the obtained B component is dissolved in 100 mL of xylene with heat, and then 50 mL of hexane and 50 mL of methanol are added to precipitate the b1 component and the b4 component that are chemically bonded or not chemically bonded to the b2 component, and b1 The b2 component not chemically bonded to the component and the b4 component was removed by filtration, and the precipitate was separated and dried.
Infrared spectra of the dried precipitate and component B were measured by FT-IR (model: NICOLET 380; manufactured by Thermo Fisher Scientific) equipped with ATR (model: Smart Orbit; manufactured by Thermo Fisher Scientific). The absorbance ratio of the absorption peak derived from b2 component (1256 cm ⁻¹ ) and the absorption peak derived from b1 component and b4 component (1376 cm ⁻¹ ) [absorbance derived from b2 component / absorbance derived from b1 component and b4 component] The grafting rate was calculated by the formula. The graft ratios of the B component were 90% for B-1, 93% for B-2, and 88% for B-3. Since the grafting rate of B-4 is the same as that of B-3, the grafting rate of B-3 is adopted, and the grafting rate of B-5 is the same as that of B-1, so that B A grafting rate of -1 was adopted.
Grafting rate (%) = (absorbance ratio of dried precipitate / absorbance ratio of surface modifier) × 100

<Preparation of foamed resin molding (foamed sheet)>
(1) Raw material A component: Thermoplastic resin (olefin resin, styrene resin)
[Olefin resin]
A-1: PF-814 (trade name; manufactured by Sun Allomer, Homo PP, MI = 3)
A-2: New Former FB3312 (trade name; manufactured by Nippon Polypro, Block PP, MI = 3)
[Styrene resin]
A-3: HH102 (trade name; manufactured by PS Japan, GPPS, MI = 3.5)
Component B: Polyorganosiloxane-modified polypropylene (surface modifier)
B-1 to B-6: <Production of component B (polyorganosiloxane-modified polypropylene)> Component C: Foaming agent C-1: Polyslen EE405F (trade name; manufactured by Eiwa Kasei Co., Ltd., sodium bicarbonate Polyethylene base MB of citric acid mixture)
C-2: Polyslen ES405 (trade name; manufactured by Eiwa Kasei Co., Ltd., polystyrene-based MB of a mixture of sodium bicarbonate and citric acid)

(2) Blending of foam sheet using olefin resin and foam sheet using styrene resin Table 2 shows the blend of foam sheet using olefin resin produced using the above raw materials. Table 3 shows the composition of the foam sheet.

(3) Production of foamed sheet using olefin resin [Examples 1 to 9, Comparative Example 1, Target 1]
The raw material 20 times the amount shown in Table 2 was stirred with a tumbler to obtain a resin composition. Next, the resin composition was subjected to a barrel temperature of 180 to 220 ° C. (C1 = 180 ° C.) using a different-direction twin screw extruder (model: TP-20T; manufactured by Thermo Plastic Industry Co., Ltd.) with a T-die (150 mm width). C2 = 220 ° C., C3 = 200 ° C.), die temperature 170 ° C., screw rotation speed 70 rpm, extrusion rate 1.5 kg / h, extruded while foaming in the atmosphere, and turned into a cooling roll with a surface temperature of 30 ° C. And rapidly cooled to obtain foam sheets (Example products 1 to 9, Comparative example product 1 and Target product 1) using an olefin resin having a thickness of 1 mm and an expansion ratio of 1.5 times.

(4) Production of foam sheet using styrene resin [Examples 10 to 16, Comparative Example 2, Target 2]
The raw material of 20 times the amount shown in Table 3 was stirred with a tumbler to obtain a resin composition. Next, the resin composition was subjected to a barrel temperature of 160 to 200 ° C. (C1 = 160 ° C.) using a different-direction twin screw extruder (model: TP-20T; manufactured by Thermo Plastic Industry Co., Ltd.) with a T-die (150 mm width). , C2 = 200 ° C., C3 = 170 ° C.), die temperature 160 ° C., screw rotation speed 70 rpm, extrusion rate 1.5 kg / h. And rapidly cooled to obtain foam sheets (Example products 10 to 16, Comparative product 2 and Target product 2) using a styrene resin having a thickness of 1 mm and an expansion ratio of 2.0 times.

<Evaluation of foamed sheet using olefin resin and foamed sheet using styrene resin>
(1) Evaluation of tackiness Foamed sheets (Example products 1 to 9, Comparative product 1 and Target product 1) using the obtained olefin resin and foamed sheets (Example products 10 to 10) using a styrene resin 16, Comparative Example Product 2 and Target Product 2) were allowed to stand at 60 ° C. for 3 days, and then the stickiness of the surface of each foamed sheet was evaluated by touch with the following evaluation criteria. The results are shown in Tables 4 and 5.
[Evaluation criteria for stickiness]
There is no stickiness on the surface. : ○
There is a little stickiness on the surface. : △
There is a feeling of stickiness on the surface. : ×

(2) Continuous Evaluation of Water Repellency of Foamed Sheet Using Olefin Resin The water repellency of the foamed sheet using olefinic resin was obtained by using the obtained olefinic resin foamed sheet (Example products 1 to 9). The surface contact angle of Comparative Example Product 1) was measured using a contact angle meter (model: CA-X; manufactured by Kyowa Interface Science Co., Ltd.), and a foamed sheet using an olefin resin without addition of B component (target) Product 1) and each resin were compared and the water repellency effect was evaluated. Here, the water repellency indicates that the larger the contact angle value, the better the water repellency.
Further, the continuous water repellency was evaluated by measuring the contact angle before and after the cleaning operation and comparing the numerical values. Here, the continuous water repellency indicates that the water repellency is continuous when there is no difference in the contact angle before and after the cleaning operation.
The washing operation was performed by wiping the surface of the foamed sheet (Examples 1 to 8, Comparative Example 1) using an olefin resin 15 times with absorbent cotton soaked in a 20-fold diluted aqueous solution of neutral detergent. The results are shown in Table 4.

(3) Continuous water repellency evaluation of foamed sheet using styrene resin The water repellency of foamed sheet using styrene resin is also “(1) Continuous water repellency of foamed sheet using olefin resin”. In the same manner as in "Evaluation", the obtained foamed sheet using the styrene resin (Example products 10 to 16 and Comparative product 2) and the foamed sheet using the styrene resin without addition of the B component (target product 2) ) Was used to evaluate the water repellency effect. The results are shown in Table 5.

(4) Evaluation of anti-friction property Foamed sheets (Example products 1-9, Comparative example 1, Target product 1) of olefin resin obtained and foamed sheets (Example products 10-16) using a styrene resin Using Comparative Example Product 2 and Target Product 2), the foamed sheets were rubbed with each other for several seconds, and the presence or absence of rubbing noise was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
[Evaluation criteria for anti-friction properties]
There is no rubbing sound. : ○
A little rubbing noise is generated. : △
A loud rubbing sound is generated. : ×

(5) Appearance Evaluation Based on the target product 1 of the obtained foamed sheet of olefin resin, the appearance of each foamed sheet (Example products 1-9, Comparative Example 1) was visually confirmed with the following evaluation criteria. did. The results are shown in Table 4.
Similarly, the foam sheet using the styrene-based resin was also visually checked with respect to the appearance of each foam sheet (Example products 10 to 16 and Comparative product 2) on the basis of the target product 2 according to the following evaluation criteria. . The results are shown in Table 5.
[Evaluation criteria for appearance]
Compared to the target product, the surface is clean with no aggregates. : ○
Compared with the target product, there are some aggregates on the surface. Within the acceptable range. : △
Compared with the target product, the surface is slightly agglomerated and rough. : ×

結果より、実施例品１〜９は、表面のべたつきがなく、持続的な撥水性を有し、且つ擦れ音防止性有する優れた発泡シートを得ることができた。また、ｂ３成分（非ラジカル重合性のポリオルガノシロキサン）を用いたＢ成分（Ｂ‐３に対してＢ‐４、Ｂ‐１に対してＢ‐５）を配合した実施例品は、ｂ３成分がｂ２成分とグラフト化していないにもかかわらず、ｂ３成分を用いていないＢ成分を配合した実施例品より、撥水性が改善され、且つ持続的な撥水性を有していた。さらに、Ｂ成分として、ｂ４成分（ポリプロピレンワックス）を配合して得られたＢ‐３、Ｂ‐４を用いた実施例品３〜８は、外観にも優れた発泡シートを得ることができた。
一方、比較例品１は、表面のべたつきがあり、継続的な撥水性を有せず、且つ擦れ音が発生し、目的とする発泡シートを得ることができなかった。

From the results, Examples 1 to 9 were able to obtain excellent foamed sheets having no stickiness on the surface, continuous water repellency, and anti-friction properties. In addition, an example product containing a B component (B-4 with respect to B-3, B-5 with respect to B-1) using a b3 component (non-radically polymerizable polyorganosiloxane) Although it was not grafted with the b2 component, the water repellency was improved and the continuous water repellency was improved as compared with the product of Example containing the B component not using the b3 component. Further, B-3 obtained by blending b4 component (polypropylene wax) as B component, Example products 3-8 using B-4 were able to obtain a foam sheet excellent in appearance. .
On the other hand, Comparative Example Product 1 had a sticky surface, did not have continuous water repellency, and generated a rubbing sound, making it impossible to obtain the intended foamed sheet.

結果より、実施例品１０〜１６は、表面のべたつきがなく、持続的な撥水性を有し、且つ擦れ音防止性有する優れた発泡シートを得ることができた。また、ｂ３成分（非ラジカル重合性のポリオルガノシロキサン）を用いたＢ成分（Ｂ‐３に対してＢ‐４、Ｂ‐１に対してＢ‐５）配合した実施例品は、ｂ３成分がｂ２成分とグラフト化していないにもかかわらず、ｂ３成分を用いていないＢ成分を配合した実施例品より、継続的な撥水性を有していた。さらに、Ｂ成分として、ｂ４成分（ポリプロピレンワックス）を配合して得られたＢ‐３、Ｂ‐４を用いた実施例品１２〜１５は、外観にも優れた発泡シートを得ることができた。
一方、比較例品２は、表面のべたつきがあり、継続的な撥水性を有せず、且つ擦れ音が発生し、目的とする発泡シートを得ることができなかった。

From the results, Examples 10 to 16 were able to obtain excellent foamed sheets having no stickiness on the surface, continuous water repellency, and anti-friction properties. In addition, the example product containing the B component (B-4 for B-3, B-5 for B-1) using the b3 component (non-radically polymerizable polyorganosiloxane) has the b3 component Although it was not grafted with the b2 component, it had a continuous water repellency as compared with the product of the example blended with the B component not using the b3 component. Furthermore, Example products 12 to 15 using B-3 and B-4 obtained by blending the b4 component (polypropylene wax) as the B component were able to obtain a foam sheet excellent in appearance. .
On the other hand, Comparative Example Product 2 had a sticky surface, did not have continuous water repellency, and generated a rubbing sound, making it impossible to obtain the intended foamed sheet.

Claims (3)

A foamed resin molded article obtained by foam-molding a resin composition containing the following components (A) to (C).
(A) Thermoplastic resin (B) (b1) Polypropylene resin and (b2) A polyorganosiloxane containing at least one silicon atom-bonded radically polymerizable functional group in one molecule is chemically bonded. Organosiloxane-modified polypropylene (C) foaming agent The foamed resin molded article according to claim 1, wherein the polyorganosiloxane-modified polypropylene (B) further contains (b3) a non-radically polymerizable polyorganosiloxane. The (B) polyorganosiloxane-modified polypropylene further comprises (b4) a polypropylene wax, and (b2) is a polyorganosiloxane-modified polypropylene formed by chemical bonding with (b1) and (b4). The foamed resin molded article according to claim 1 or 2.