JP2009215523A - Alcohol-resistant molding material, and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alcohol-resistant molding material, which have good alcohol resistance, mechanical strength, and ultrasonic welding property, and is suitable for use under conditions where it contacts with alcohol, and to provide an article molded using the material. <P>SOLUTION: The alcohol-resistant molding material contains a 35-77 mass% component (A), a 7-40 mass% component (B), a 15-50 mass% component (C), and a 0.1-15 mass% component (D), wherein the component (A) is an olefinic resin, the component (B) is a rubber-reinforced resin containing a graft copolymer (B1) obtained by polymerization of a vinylic monomer (b) in the presence of ethylene-α-olefin rubber (a1) and/or hydrogenated conjugated diene rubber (a2), the component (C) is a glass fiber converged using a converging agent comprising a copolymer (c1) of an aromatic vinyl compound and a vinyl cyanide compound, and an epoxy resin (c2) or an urethane polymer (c3), and the component (D) is an acid-modified olefinic resin with an acid number of 5-40. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a molding material for a molded article that requires alcohol resistance, such as a container that contains alcohol, and a molded article such as an alcohol container that is molded with the molding material. However, it has excellent chemical resistance with less occurrence of defects such as whitening, cracking, deformation, etc., and alcohol resistance molding with excellent mechanical strength and ultrasonic weldability in addition to permeation resistance to alcohol and heat resistance in the presence of alcohol. The present invention relates to a material and a molded product such as an alcohol container molded with the material.

  In recent years, various resin molded products used in fuel cells and the like have been required to have excellent chemical resistance, heat resistance, and the like. Here, the fuel cell includes electrodes on both sides of an electrolyte that is an ionic conductor, supplies an oxidizing gas such as oxygen or air to one electrode, and gaseous fuel such as hydrogen or hydrocarbons to the other electrode, or It is a battery that supplies liquid fuel such as alcohol and generates electricity and water by causing an electrochemical reaction between these electrodes.

  A direct methanol fuel cell (DMFC) that directly supplies methanol as a fuel can use a solid polymer electrolyte membrane as an electrolyte, and therefore may operate at 100 ° C. or lower, and the fuel is liquid and transported. Since it is easy to store, it is considered to be suitable for small size and portable use, and it is regarded as promising as a power source for future automobile power sources and mobile electronic devices. The structure of DMFC is disclosed in Patent Document 1, for example.

  Further, Patent Document 2 discloses a method for using a fuel cell as a power source for a portable electronic device. According to this method, fuel is supplied from a replaceable cartridge in which a small DMFC is incorporated in a portable electronic device and filled with methanol.

  As materials for forming the cartridge, Patent Document 1 describes acrylic resin, and Patent Document 2 describes polypropylene and polyethylene. Further, Patent Document 3 describes a fuel container or cartridge for an alcohol direct fuel cell made of a polyphenylene ether resin and a polyolefin resin, and a polyphenylene ether resin and a polystyrene resin.

JP 2003-17102 A JP 2003-92128 A JP 2005-222845 A

Alcohol container molding material and the performance of the alcohol container molded with it are excellent in chemical resistance with less occurrence of defective phenomena such as whitening, cracking, deformation, etc. even when the alcohol comes into contact with the container. In order to prevent alcohol from leaking out of the container, it is excellent in permeation resistance to alcohol, and it is required to maintain sufficient heat resistance even when used in the presence of alcohol at a high use environment temperature. Moreover, high mechanical strength is calculated | required from a viewpoint of the robustness of a container. And in a container manufacturing process, it is calculated | required that it is excellent in the ultrasonic welding property which overlap | superposes resin and metals, superposes | vibrates ultrasonically, generates frictional heat by rubbing each other, melts and adheres.
However, the compositions disclosed in Patent Documents 1 to 3 have insufficient chemical resistance, permeation resistance, heat resistance in the presence of alcohol, mechanical strength, and ultrasonic weldability, and the range of use thereof is It was limited.

  The present invention is excellent in chemical resistance with few occurrences of defective phenomena such as whitening, cracking and deformation even in contact with alcohol, permeation resistance to alcohol, heat resistance in the presence of alcohol, impact strength, bending strength, etc. An object of the present invention is to provide an alcohol-resistant molding material and molded article excellent in mechanical strength and ultrasonic weldability.

  As a result of intensive studies to solve the above problems, the present inventors have found that the olefin resin (A), the specific graft copolymer (B), the specific convergent glass fiber (C), and the specific The molding material containing a specific amount of each of the acid-modified olefin resin (D) is a problem of the above-mentioned mechanical resistance such as chemical resistance, permeation resistance, heat resistance, impact strength, bending strength, and ultrasonic weldability. The present inventors have found that a molded product that eliminates the problem can be obtained, and have completed the present invention.

That is, the present invention is shown below.
1. The following component (A) 35-77 mass%, the following component (B) 7-40 mass%, the following component (C) 15-50 mass%, and the following component (D) 0.1-15 mass%. Alcohol-resistant molding material to be contained (however, the total of the components (A), (B), (C) and (D) is 100% by mass).
Component (A): Olefin resin;
Component (B): In the presence of the rubbery polymer (a) comprising the ethylene-α-olefin rubber (a1) and / or the hydrogenated conjugated diene rubber (a2), the vinyl monomer (b) is added. A rubber-reinforced resin comprising a graft copolymer (B1) obtained by polymerization, or a mixture of the graft copolymer (B1) and a (co) polymer (B2) of a vinyl monomer (b);
Component (C): selected from the group consisting of a vinyl monomer copolymer (c1) containing an aromatic vinyl compound and a vinyl cyanide compound, an epoxy resin (c2) and a urethane polymer (c3) Glass fibers converged with at least one sizing agent;
Component (D): An acid-modified olefin resin having an acid value of 5 to 40.
2. 2. The alcohol-resistant molding material according to 1, wherein the component (D) is an olefin resin modified with maleic acid and / or maleic anhydride.
3. 3. A molded product molded from the alcohol-resistant molding material according to 1 or 2 above. 4. The molded article according to 3 above, which is an alcohol container.

  Molded articles molded with the alcohol-resistant molding material of the present invention have excellent chemical resistance with little occurrence of defects such as whitening, cracking and deformation even when in contact with alcohol, and excellent permeation resistance to alcohol. It has heat resistance in the presence of sufficient alcohol for use at ambient temperatures. Moreover, it is excellent in mechanical strength, such as impact strength and bending strength, and is also excellent in ultrasonic weldability in the container manufacturing process. Therefore, it is extremely useful as a molding material for a molded product used under conditions in contact with alcohol, such as a fuel container (including a cartridge) for an alcohol direct fuel cell.

  The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

  The alcohol-resistant molding material of the present invention comprises an olefin resin (A), a specific graft copolymer (B), a specific glass fiber (C), and a specific acid-modified olefin resin (D). It is contained as an essential component. Hereinafter, each component will be described in detail.

Ingredient (A)
The component (A) used in the present invention is an olefin resin, and typically comprises at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 10 carbon atoms. It is a polymer contained as a body unit. As this olefin resin, those showing crystallinity at room temperature by X-ray diffraction are preferred, more preferably the crystallinity is 20% or more, and the melting point is preferably 40 ° C. or more. The olefin resin preferably has sufficient strength for use at room temperature and sufficient moldability for injection molding, for example.

  Examples of olefins that are constituent monomer units of the component (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1- There are pentene, 3-methyl-1-hexene, 1-octene and the like, preferably ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and 1-octene. In addition, other single quantities such as non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene, etc. The body component can be used as a part of the constituent monomer unit.

  As the component (A), ionomers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, cyclic olefin copolymers, chlorinated polyethylene, brominated polyethylene and the like can also be used.

  The component (A) used in the present invention may be a homopolymer or a copolymer, and the copolymer may be either a random copolymer or a block copolymer. Of these, propylene homopolymer and ethylene-propylene block copolymer are particularly preferred.

  For example, the polypropylene resin as the component (A) preferably has a melt flow rate (MFR) measured under the conditions of 230 ° C. and 2.16 kg of 0.01 to 500 g / 10 minutes, more preferably 0.05 to 100 g / 10 min.

Ingredient (B)
The component (B) used in the present invention comprises a vinyl polymer in the presence of a rubbery polymer (a) comprising an ethylene-α-olefin rubber (a1) and / or a hydrogenated conjugated diene rubber (a2). Graft copolymer (B1) obtained by polymerizing monomer (b) or a mixture of graft copolymer (B1) and (co) polymer (B2) of vinyl monomer (b) It is a rubber reinforced resin consisting of

Graft copolymer (B1)
The graft copolymer (B1) constituting the rubber-reinforced resin of the component (B) is a rubbery polymer comprising an ethylene-α-olefin rubber (a1) and / or a hydrogenated conjugated diene rubber (a2) ( It is obtained by polymerizing the vinyl monomer (b) in the presence of a).
Examples of the ethylene-α-olefin rubber (a1) include an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer. Examples of the α-olefin constituting the component (a1) include α-olefins having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in admixture of two or more. The carbon number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. If the number of carbon atoms exceeds 20, the copolymerizability is lowered and the surface appearance of the molded product may not be sufficient. The mass ratio of ethylene / α-olefin is preferably 5 to 95/95 to 5, more preferably 50 to 90/50 to 10, and still more preferably 60 to 88/40 to 12. When the α-olefin mass ratio exceeds 95, the weather resistance is not sufficient. On the other hand, when it is less than 5, the rubber elasticity of the rubbery polymer is not sufficient, so that sufficient impact resistance may not be exhibited. .

Non-conjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, with 5-ethylidene-2-norbornene and dicyclopentadiene being preferred. These non-conjugated dienes can be used alone or in admixture of two or more. The ratio of the nonconjugated diene to the total amount of the rubbery polymer is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 10% by mass. If the proportion of the non-conjugated diene exceeds 30% by mass, the molded appearance and weather resistance may not be sufficient. In addition, the amount of unsaturated groups in component (a1) is preferably in the range of 4 to 40 in terms of iodine value.
Moreover, the Mooney viscosity (ML1 _{+ 4} , 100 degreeC; based on JISK6300) of a component (a1) becomes like this. Preferably it is 5-80, More preferably, it is 10-65, More preferably, it is 15-45. When the Mooney viscosity exceeds 80, the fluidity is insufficient, and when the Mooney viscosity is less than 5, the resulting molded article may have insufficient impact resistance.

  Examples of the hydrogenated conjugated diene rubber (a2) include hydrogenated products of conjugated diene block copolymers having the following structure. That is, polymer block A composed of aromatic vinyl compound units, and the double bond portion of a polymer composed of conjugated diene compound units having a 1,2-vinyl bond content exceeding 25 mol% are hydrogenated at 80 mol% or more. Polymer block B, polymer block C obtained by hydrogenating at least 80 mol% of a double bond portion of a polymer comprising a conjugated diene compound unit having a 1,2-vinyl bond content of 25 mol% or less, and an aroma A block copolymer comprising a combination of two or more of polymer blocks D formed by hydrogenating a double bond portion of a copolymer of an aromatic vinyl compound unit and a conjugated diene compound unit in an amount of 80 mol% or more. is there.

  Examples of the aromatic vinyl compound used in the production of the polymer block A include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, pt- Examples thereof include butyl styrene, ethyl styrene and vinyl naphthalene, and these can be used alone or in combination of two or more. Of these, styrene is preferred. The proportion of the polymer block A in the block copolymer is preferably 0 to 65% by mass, more preferably 10 to 40% by mass in the block copolymer. When the polymer block A exceeds 65% by mass, the impact resistance may not be sufficient.

  The polymer blocks B, C and D can be obtained by hydrogenating a polymer of a conjugated diene compound. Examples of the conjugated diene compounds used for the production of the polymer blocks B, C and D include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, etc., but can be used industrially and have physical properties. In order to obtain an excellent hydrogenated diene rubber polymer, 1,3-butadiene and isoprene are preferred. These can be used individually by 1 type or in mixture of 2 or more types. Examples of the aromatic vinyl compound used in the production of the polymer block D include the same aromatic vinyl compounds used in the production of the polymer block A, and these may be used alone or in combination of two types. The above can be mixed and used. Of these, styrene is preferred.

  The hydrogenation rate of the polymer blocks B, C and D is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. If it is less than 80 mol%, the weather resistance may be lowered. The 1,2-vinyl bond content of the polymer block B is preferably more than 25 mol% and 90 mol% or less, and more preferably 30 to 80 mol%. If the 1,2-vinyl bond content of the polymer block B is 25 mol% or less, rubber properties may be lost and impact resistance may not be sufficient, whereas if it exceeds 90 mol%, chemical resistance May not be sufficient. Further, the 1,2-vinyl bond content of the polymer block C is preferably 25% by mole or less, and more preferably 20% by mole or less. When the 1,2-vinyl bond content of the polymer block C exceeds 25 mol%, scratch resistance and sliding properties may not be sufficiently exhibited. The 1,2-vinyl bond content of the polymer block D is preferably 25 to 90 mol%, more preferably 30 to 80 mol%. If the 1,2-vinyl bond content of the polymer block D is less than 25 mol%, rubber properties may be lost and impact resistance may not be sufficient. On the other hand, if it exceeds 90 mol%, May not be sufficient. The aromatic vinyl compound content of the polymer block D is preferably 50% by mass or less, and more preferably 30% by mass or less. If the content of the aromatic vinyl compound in the polymer block D exceeds 50% by mass, rubber properties may be lost and impact resistance may not be sufficient.

The molecular structure of the block copolymer may be branched, radial, or a combination thereof, and the block structure may be a diblock, a triblock, a multiblock, or a combination thereof. For example, A- (BA) _n , (AB) _n , A- (BC) _n , C- (BC) _n , (BC) _n , A- (DA) _n , (AD) _n , A- (DC) _n , C- (DC) _n , (DC) _n , A- (BCD) _n , (AB) C-D) _n , where n is an integer equal to or greater than 1, and is preferably a block copolymer, preferably ABA, ABBA, ABBC, It is a block copolymer having a structure of A-D-C or C-B-C.
The weight average molecular weight (Mw) of the components (a1) and (a2) is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and more preferably 50,000 to 500,000. If the Mw is less than 10,000, the impact resistance is not sufficient, while if it has a high molecular weight exceeding 1 million, the appearance of the molded product may not be sufficient.

  The vinyl monomer (b) is at least one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, and other copolymerizable other vinyl monomers. The vinyl monomer (b) usually contains an aromatic vinyl compound and a vinyl cyanide compound as essential components, and if necessary, contains other copolymerizable other vinyl monomers. Become. The amount of other copolymerizable vinyl monomers used is within the range not impairing the effects of the present invention, and is preferable when the entire vinyl monomer (b) is 100% by mass. Is 0 to 95% by mass, more preferably 5 to 95% by mass, and still more preferably 15 to 90% by mass.

  Examples of the aromatic vinyl compound include those similar to the aromatic vinyl compound used in the production of the polymer block A of the conjugated diene block copolymer, and these may be used alone or in combination of two or more. It can also be used. A preferred aromatic vinyl compound is styrene or an aromatic vinyl compound containing 50% by mass or more of styrene. The amount of the aromatic vinyl compound used is preferably 5 to 80% by mass, more preferably 8 to 70% by mass, based on the entire vinyl monomer (b). If the amount of the aromatic vinyl compound used is less than 5% by mass, the resin moldability and thermal stability are not sufficient. On the other hand, if it exceeds 80% by mass, sufficient resin toughness may not be obtained.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. The amount of the vinyl cyanide compound used is preferably 3 to 50% by mass, more preferably 5 to 35% by mass, based on the entire vinyl monomer (b). If the amount of vinyl cyanide compound used is less than 3% by mass, the chemical resistance is not sufficient. On the other hand, if it exceeds 50% by mass, for example, the surface appearance of the molded product and the thermal stability of the resin may not be sufficient. is there.

  The other copolymerizable vinyl monomer is not particularly limited as long as it is copolymerizable with an aromatic vinyl compound and / or a vinyl cyanide compound. For example, alkyl (meth) acrylate Examples thereof include esters, maleimide group-containing unsaturated compounds, and various other functional group-containing unsaturated compounds.

  Examples of (meth) acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and other acrylic acid alkyl esters, methyl methacrylate, ethyl methacrylate Methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate and cyclohexyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types. When (meth) acrylic acid alkyl ester is used, transparency or transparency is imparted. When using (meth) acrylic-acid alkylester, the usage-amount is in the (b) component, Preferably it is 1-80 mass%, More preferably, it is 5-80 mass%.

  Examples of the maleimide group-containing unsaturated compound include maleimide compounds such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. These can be used individually by 1 type or in combination of 2 or more types. The maleimide compound may be introduced by a method in which maleic anhydride is copolymerized and then imidized. When a maleimide group-containing unsaturated compound is used, heat resistance is imparted. When using a maleimide group containing unsaturated compound, the usage-amount is in the (b) component, Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.

  Other various functional group-containing unsaturated compounds include carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, substituents or unsubstituted amino groups Examples include unsaturated compounds and oxazoline group-containing unsaturated compounds. These functional group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the acid anhydride group-containing unsaturated compound include unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples thereof include methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, and N-vinyl. Examples include diethylamine, N-acetylvinylamine, acrylic amine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, and p-aminostyrene. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These can be used individually by 1 type or in combination of 2 or more types.

When such a functional group-containing unsaturated compound is used, when the rubber reinforced resin and another polymer are blended, the compatibility between the two can be improved. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated compounds, more preferably hydroxyl group-containing unsaturated compounds, particularly preferably. 2-hydroxylethyl (meth) acrylate.
The amount of the functional group-containing unsaturated compound used is the total amount of the functional group-containing unsaturated compounds used in the rubber reinforced resin, and is preferably 0.01 to 20% by mass with respect to the entire rubber reinforced resin. 0.01-10 mass% is preferable with respect to the whole thermoplastic resin composition, and 0.05-5 mass% is further more preferable.

  In the present invention, the vinyl monomer (b) usually contains an aromatic vinyl compound and a vinyl cyanide compound as essential components, and, if necessary, other copolymerizable other vinyl monomers. Containing. More preferably, the vinyl monomer (b) contains an aromatic vinyl compound and a vinyl cyanide compound as essential components, and if necessary, from a (meth) acrylic acid alkyl ester and a maleimide group-containing unsaturated compound. At least one vinyl monomer selected from the group consisting of:

The amount of the rubbery polymer (a) used is preferably 5 to 60% by mass and more preferably 5 to 55% by mass with respect to 100% by mass in total of the component (a) and the component (b). When the amount of the component (a) used is less than 5% by mass, the impact resistance is not sufficient. On the other hand, when it exceeds 60% by mass, the moldability, the heat distortion temperature, the heat resistance in the presence of alcohol, and the rigidity are sufficient. There is a possibility of disappearing.
On the other hand, the amount of the vinyl monomer (b) used is preferably 40 to 95% by mass, more preferably 45 to 95% by mass with respect to 100% by mass in total of the component (a) and the component (b). It is. When the amount of the component (b) used exceeds 95% by mass, the impact resistance is not sufficient. On the other hand, when it is less than 40% by mass, the molding processability, heat distortion temperature, heat resistance in the presence of alcohol, and rigidity are low. It may not be enough.

  The graft ratio of the component (B1) is usually 10 to 200%, preferably 20 to 120%, more preferably 30 to 90%. If the graft ratio is less than 10%, the impact strength is not sufficient. On the other hand, if it exceeds 200%, the balance between the impact resistance and the appearance of the molded product may not be sufficient. The graft ratio can be easily adjusted by the kind and amount of the polymerization initiator, the polymerization temperature, the amount of the monomer, and the like.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the component (B1) is 0.2 to 1.5 dl / g, preferably 0.25 to 1.0 dl / g. More preferably, it is 0.3 to 0.8 dl / g. When the intrinsic viscosity [η] is less than 0.2 dl / g, the impact strength of the molded product is not sufficient. On the other hand, when it exceeds 1.5 dl / g, the gloss of the molded product surface decreases and the occurrence of flow marks occurs. May be incurred. The intrinsic viscosity [η] can be easily controlled by changing the type and amount of the polymerization initiator, chain transfer agent, emulsifier, solvent, and the like, as well as the polymerization time and polymerization temperature.

  This graft ratio (mass%) is calculated | required by following Formula (1).

  Graft ratio (% by mass) = {(TS) / S} × 100 (1)

  In the above formula (1), T is charged with 1 g of component (B1) in 20 ml of acetone, shaken with a shaker for 2 hours, and then centrifuged for 60 minutes with a centrifuge (rotation speed: 23,000 rpm). It is the mass (g) of the insoluble matter obtained by separating the insoluble matter and the soluble matter, and S is the mass (g) of the component (a) contained in 1 g of the component (B1).

  The intrinsic viscosity [η] of the copolymer was measured by the following method. First, the copolymer was dissolved in methyl ethyl ketone to prepare 5 samples having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.

  The component (B1) can be produced by subjecting the component (b) to radical graft polymerization by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization or the like in the presence of the component (a). Of these, emulsion polymerization and solution polymerization are preferred. In the radical graft polymerization, a commonly used polymerization solvent (in the case of solution polymerization), polymerization initiator, chain transfer agent, emulsifier (in the case of emulsion polymerization), and the like can be used. In addition, the monomer component used to produce the component (B1) may be polymerized by adding the monomer component all at once in the presence of the total amount of the rubbery polymer, or may be divided or continuously added. Polymerization may be performed. Moreover, you may superpose | polymerize by the method of combining these. Furthermore, all or part of the rubber-like polymer may be added and polymerized during the polymerization.

  The solvent used in the solution polymerization method is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, dichloromethylene, carbon tetrachloride, etc. Organic solvents such as halogenated hydrocarbons are used. The amount of the solvent used is preferably 20 to 200 parts by mass, more preferably 50 to 150 parts by mass, with respect to 100 parts by mass of the total amount of the components (a) and (b).

  As the polymerization initiator, a general initiator suitable for the polymerization method is used. As the polymerization initiator for solution polymerization, for example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, and the like can be used. The polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator used is preferably 0.05 to 2% by mass, more preferably 0.2 to 0.8% by mass, based on the monomer component.

  Examples of the polymerization initiator for emulsion polymerization include organic hydroperoxides typified by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and the like, a sugar-containing pyrophosphate formulation, and a sulfoxylate formulation. A redox system in combination with a reducing agent represented by the above or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide, or the like can be used. Of these, organic hydroperoxides represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, etc., and reducing agents represented by sugar-containing pyrophosphate formulation, sulfoxylate formulation, etc. Redox system by combination with is good. The initiator may be oil-soluble or water-soluble, and may be used in combination of oil-solubility and water-solubility. The addition ratio of the water-soluble initiator when combined is preferably 50% by mass or less, more preferably 25% by mass or less of the total addition amount. Furthermore, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator used is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 0.7% by mass, based on the monomer component.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, tetrachloride. Examples thereof include hydrocarbons such as carbon, ethylene bromide and pentaphenylethane, or dimer of acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, and α-methylstyrene. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divided addition, or continuous addition. The amount of the chain transfer agent used is preferably about 0 to 5% by mass with respect to the monomer component.

  Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, examples of the anionic surfactant include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, and fatty acid salts. Further, as the nonionic surfactant, an ordinary polyethylene glycol alkyl ester type, alkyl ether type, alkylphenyl ether type, or the like is used. Further, examples of the amphoteric surfactant include those having a carboxylate, sulfate ester, sulfonate, and phosphate ester salt as the anion moiety, and an amine salt, quaternary ammonium salt, and the like as the cation moiety. The amount of the emulsifier is preferably 0.3 to 5% by mass with respect to the monomer component. In addition, the polymerization temperature in the case of graft polymerization becomes like this. Preferably it is 10-160 degreeC, More preferably, it is 30-120 degreeC.

In the graft copolymer (B1) of the present invention obtained by copolymerizing the vinyl monomer (b) in the presence of the rubber polymer (a), the vinyl monomer component usually contains a rubber heavy polymer. The copolymer grafted to the union and the ungrafted component in which the vinyl monomer component is not grafted to the rubber polymer (that is, the same vinyl monomer (b) as the following component (B2) ( Co) polymers) and ungrafted rubbery polymers (a).
Component (B1) comprises (i) a graft copolymer obtained by polymerizing vinyl monomer (b) in the presence of rubber polymer (a) comprising component (a1), (ii) A graft copolymer obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) comprising the component (a2), and (iii) the component (a1) and the above It includes at least three embodiments of a graft copolymer obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) comprising the component (a2). The rubber-reinforced resin of component (B) includes a mode in which the graft copolymer (ii) or (i) is mixed with the graft copolymer (i) or (ii), respectively. It is what

(Co) polymer (B2) of vinyl monomer (b)
The rubber-reinforced resin of the component (B) may be a mixture of the graft copolymer (B1) and the (co) polymer (B2) of the vinyl monomer (b).
The (co) polymer (B2) is obtained by polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a).
Examples of the vinyl monomer (b) constituting the (co) polymer (B2) include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimides described for the component (B1). All group-containing unsaturated compounds and other various functional group-containing unsaturated compounds can be used. These compounds can be used alone or in combination of two or more. Usually, an aromatic vinyl compound and a vinyl cyanide compound are essential monomer components, and if necessary, one kind selected from the group consisting of (meth) acrylic acid alkyl esters and maleimide group-containing unsaturated compounds The above can be used together as a monomer component, and if necessary, at least one of various other functional group-containing unsaturated compounds can be used as a monomer component.
In order to improve the compatibility between the rubber-reinforced resin (B) and other components, an epoxy group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, or a hydroxyl group-containing unsaturated compound is used as the functional group-containing unsaturated compound. Of these, a hydroxyl group-containing unsaturated compound is more preferable, and 2-hydroxylethyl (meth) acrylate is particularly preferable.

The preferred use amount of the aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid alkyl ester and maleimide group-containing unsaturated compound in the component (b) is the same as the use amount in the component (B1).
Preferred monomer combinations of (co) polymer (B2) include (a) aromatic vinyl compound / vinyl cyanide compound, (b) aromatic vinyl compound / (meth) acrylic acid alkyl ester, (c) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid alkyl ester, (d) aromatic vinyl compound / maleimide compound / vinyl cyanide compound, and (e) aromatic vinyl compound / 2-hydroxylethyl (meta ) Acrylate / vinyl cyanide compound.

The (co) polymer (B2) can be produced by the same method as the component (B1) except that the vinyl monomer (b) is polymerized in the absence of a rubbery polymer.
The (co) polymer (B2) may be a (co) polymer having a single composition, or a blend of two or more (co) polymers having different compositions.
The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the (co) polymer (B2) is usually 0.3 to 1.5, preferably 0.3 to 1.3 dl / g, More preferably, it is 0.4-1.0 dl / g, Most preferably, it is 0.4-0.8 dl / g. This intrinsic viscosity can be controlled by chain transfer agent, polymerization time, polymerization temperature, and the like.
The (co) polymer (B2) can be mixed with the component (B1) by an appropriate method.

  The content of the rubbery polymer (a) in the component (B) is preferably 3 to 45% by mass, more preferably 5 to 40% by mass, particularly preferably 100% by mass of the component (B). 5 to 35% by mass. Content of a component (a) can be easily adjusted by changing the compounding quantity of the said component (B2). Component (B2) may be blended in advance with component (B), or when the components (A), (B), (C) and (D) are mixed to prepare the molding material of the present invention. You may mix with these components.

Ingredient (C)
The component (C) used in the present invention is composed of a vinyl monomer copolymer (c1), an epoxy resin (c2) and a urethane polymer (c3) containing an aromatic vinyl compound and a vinyl cyanide compound. A glass fiber converged with at least one sizing agent selected from the group consisting of:

As the aromatic vinyl compound used as a constituent monomer of the copolymer (c1), compounds listed as the aromatic vinyl compound of the component (B) can be used, and preferably styrene, α-methyl Styrene, more preferably styrene.
As the vinyl cyanide compound used as a constituent monomer of the copolymer (c1), compounds listed as the vinyl cyanide compound of the component (B) can be used, and acrylonitrile is preferable.
The use ratio (aromatic vinyl compound / vinyl cyanide compound) of the aromatic vinyl compound and the vinyl cyanide compound in the copolymer (c1) is preferably 50 to 95/5 to 50 (mass ratio), and 55 to 90. / 10 to 45 (mass ratio) is more preferable. As the copolymer (c1), usually, a copolymer (AS resin) composed of two components of an aromatic vinyl compound and a vinyl cyanide compound is suitably used. An epoxy group-containing unsaturated compound is used as a comonomer. The epoxy-modified AS resin contained may be sufficient. As the epoxy group-containing unsaturated compound, the compounds listed as the epoxy group-containing unsaturated compound of component (B) can be used.

  As said epoxy resin (c2), the well-known epoxy resin currently used as a sizing agent of glass fiber is mentioned.

  As said urethane type polymer (c3), the well-known urethane type polymer currently used as a sizing agent of glass fiber is mentioned.

Examples of the glass composition of the glass fiber of the component (C) include silicate glass, borosilicate glass, and phosphate glass. Examples of the glass include E glass, C glass, A glass, S glass, M glass, AR glass, and L glass, and E glass and C glass are preferable.
The glass fiber is preferably treated with both a sizing agent and a silane coupling agent. A silane coupling agent can surface-treat glass fiber, for example, before converging glass fiber with a sizing agent. In this case, the chemical resistance, permeation resistance, heat resistance, mechanical strength such as impact strength and bending strength, and ultrasonic weldability of the molded product are further improved.
As the silane coupling agent, the formula Y—R—Si— (X) ₃ (wherein Y represents a vinyl group, amino group, epoxy group, methacryl group or mercapto group, and R represents a divalent organic group). Or may be absent, and X represents an alkoxy group, an alkyl group, an acetoxy group, or a chloro atom). X is preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group. Of the compounds of the above formula, Y is an aminosilane, an amino group, Y is a vinylsilane, and Y is a mercaptosilane, and aminosilane is particularly preferable. Specific examples of aminosilane include 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3 -Aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

The amount of the sizing agent used is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 0.5 to 6% by mass in terms of solid content with respect to the glass fiber. preferable.
Moreover, in order to improve the adhesiveness of glass fiber and resin, you may use a silane coupling agent etc. together. Examples of the silane coupling agent include known silane coupling agents. The usage-amount of a silane coupling agent is about 0.01-20 mass% with respect to a sizing agent. The converging glass fiber of the present invention is preferably in the form of chopped land obtained by twisting a plurality of long fibers having a small diameter and converging them with a converging agent.
1-10 mm is preferable, as for the average length before mixing of the convergence glass fiber of the component (C) of this invention, 2-6 mm is more preferable, and 5-25 micrometers is preferable and an average diameter is 8-20 micrometers more. preferable.
The residual average fiber length of the component (C) dispersed in the molded product molded from the molding material of the present invention is preferably 150 to 1000 μm, more preferably 200 to 800 μm, and even more preferably 250 to 700 μm. When the residual average fiber length is in the above range, a molded article having a much higher rigidity at high temperatures can be obtained.
The residual average fiber length is measured by cutting out a part of the molded product. Specifically, the cut molded product is heated to 800 ° C. to decompose the resin component, and then the fiber length of the remaining glass fiber is measured by image analysis.

Ingredient (D)
Component (D) used in the present invention is an acid-modified olefin resin having an acid value of 5 to 40.
Examples of the olefin resin include homopolymers of olefins, block copolymers, and mixtures thereof. Specific examples include propylene homopolymers, ethylene homopolymers, and ethylene-propylene block copolymers. Among these, a propylene homopolymer and an ethylene-propylene block copolymer are preferable.
The acid modification of component (D) means that an acid group is imparted to an olefin resin by bonding a compound having an acid group, and examples of compounds that can be used for acid modification include acrylic acid and methacrylic acid. Examples thereof include unsaturated acids such as acid, crotonic acid, itaconic acid and maleic acid, and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, chloromaleic anhydride and citraconic anhydride. These unsaturated acids or unsaturated acid anhydrides can be used alone or in combination of two or more. Of these unsaturated acids or unsaturated acid anhydrides, maleic acid and maleic anhydride are preferred. Accordingly, the acid-modified olefin resin is preferably an olefin resin having a maleic acid group and / or a maleic anhydride group.
The acid value of a component (D) is 5-40, Preferably it is 10-35, More preferably, it is 12-35. The acid value is measured according to JIS K 0760. When the acid value is less than 5, the affinity with the glass fiber is inferior, and as a result, the mechanical strength is inferior. On the other hand, when the acid value exceeds 40, the affinity with methanol increases, and as a result, the heat distortion temperature is inferior.
Examples of commercially available products corresponding to the component (D) include Umex 1001, Umex 1003, and Umex 2000 (trade name: maleic acid-modified olefin resin manufactured by Sanyo Chemical Industries, Ltd.).

Production of Alcohol-Resistant Molding Material The alcohol-resistant molding material of the present invention is obtained by mixing the components (A), (B), (C) and (D) at a predetermined blending ratio.

  The component (A) is useful for improving the alcohol resistance of the molding material of the present invention, and the blending amount is the sum of the components (A), (B), (C) and (D). As 100 mass%, it is 35-77 mass%, Preferably it is 40-70 mass%, More preferably, it is 45-70 mass%. When the blending amount is less than 35% by mass, the alcohol resistance is inferior, and when it exceeds 77% by mass, the impact resistance is inferior.

  The component (B) is useful for improving the impact resistance of the molding material of the present invention, and the blending amount thereof is the sum of the components (A), (B), (C) and (D). As 100 mass%, it is 7-40 mass%, Preferably it is 10-30 mass%, More preferably, it is 10-25 mass%. When the blending amount is less than 7% by mass, the impact resistance is inferior, and when it exceeds 40% by mass, the alcohol resistance is inferior, and the heat distortion resistance at 50 ° C. is inferior.

  The component (C) is useful for improving the rigidity at a high temperature of the molding material of the present invention, specifically, the bending maximum stress at 50 ° C. and the bending elastic modulus at 50 ° C. The total of the components (A), (B), (C), and (D) is 15 to 50% by mass, preferably 19 to 45% by mass, more preferably 19 to 40%, based on 100% by mass. % By mass. When the blending amount is less than 15% by mass, the rigidity at high temperatures is inferior, and when it exceeds 50% by mass, the appearance of the molded product and the ultrasonic weldability are inferior.

  The component (D) is useful for improving the rigidity at a high temperature of the molding material of the present invention, specifically, the bending maximum stress at 50 ° C. and the bending elastic modulus at 50 ° C. The total of the components (A), (B), (C) and (D) is 0.1 to 15% by mass, preferably 0.5 to 14% by mass, more preferably 100% by mass. Is 0.5-13 mass%. When the amount is less than 0.1% by mass, the rigidity is inferior, and when it exceeds 15% by mass, the rigidity, the permeation resistance to alcohol, and the heat resistance in the presence of alcohol are inferior.

  In addition, the alcohol-resistant molding material of the present invention includes a filler other than the component (C), a lubricant, a heat stabilizer, an antioxidant, a heat conductive filler, an ultraviolet absorber, a flame retardant, and anti-aging as necessary. Various additives such as an agent, a plasticizer, an antibacterial agent, and a colorant can be contained within a range not impairing the object of the present invention.

  Furthermore, the alcohol-resistant molding material of the present invention can contain other resins, for example, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyamide, and the like, if necessary, within a range that does not impair the object of the present invention. .

  The alcohol-resistant molding material of the present invention is prepared by mixing each component at a predetermined mixing ratio using a tumbler mixer, a Henschel mixer, or the like, and then, such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, It can be produced by melt-kneading under suitable conditions using a mixer. A preferred kneader is a twin screw extruder. Furthermore, when each component is kneaded, each component may be kneaded in a lump or may be kneaded in multiple stages. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. Moreover, it is more preferable to supply the fibrous thing among fillers from the middle of an extruder with a side feeder in order to prevent the cutting | disconnection in kneading | mixing. The melt kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.

  The alcohol-resistant molding material of the present invention thus obtained can be molded into various molded products by injection molding, sheet extrusion, vacuum molding, profile extrusion, foam molding, injection press, press molding, blow molding and the like. . The alcohol-resistant molding material of the present invention is excellent in chemical resistance with less occurrence of defects such as whitening, cracking and deformation even when in contact with alcohol, permeation resistance to alcohol, heat resistance in the presence of alcohol, machine Products with excellent mechanical strength and ultrasonic weldability. Utilizing these characteristics, various parts and housings in the OA / home appliance field, electrical / electronic field, sundries field, sanitary field, automobile field, etc. Can be used for chassis, tray, etc. Among these, it is suitable for a container (including a cartridge) for storing alcohol of an alcohol direct fuel cell.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited at all to the following Example, unless the summary is exceeded. In the examples, parts and% are based on mass unless otherwise specified.

(1) Evaluation method Measurement methods for various evaluation items in the following Examples and Comparative Examples are shown below.
(1-1) Physical property test: Measured at 50 ° C. using a precision universal testing machine “Autograph AG5000E type” manufactured by Shimadzu Corporation in accordance with the maximum bending stress / flexural modulus ISO178. The unit of the measured value is MPa.

(1-2) Physical property test: Charpy impact strength (Edgewise Impact, notched) at room temperature was measured according to Charpy impact strength ISO179. The measurement conditions are
Specimen type: Type 1
Notch type: Type A
Load: 2J
The unit is KJ / m ² .

(1-3) Physical property test: Heat distortion temperature (HDT)
According to ISO75, the measurement was performed under a load of 1.80 MPa. The unit of measurement is ° C.

(1-4) Methanol resistance test: Gas barrier property (cup test)
As shown in FIG. 1, 10 g of methanol 2 is put in a metal cylindrical cup 1 having a diameter of 60 mm, and the opening of the cup 1 is a disc-shaped test piece 3 having a thickness of 1 mm and a diameter of 74 mm. Sealed to prevent leakage. And after leaving to stand in a 50 degreeC thermostat for 5 days, this was taken out and the reduction | decrease amount (%) of methanol was measured. The measurement result shows that the smaller the amount of methanol decrease, the better the permeation resistance of the molding material to methanol.

(1-5) Methanol resistance test: 50 ° C. heat distortion resistance (cup test)
In the gas barrier property test of (1-4) above, the amount of deformation (mm) upward of the center of the test piece when taken out from the thermostat was measured. The measurement results show that the smaller the amount of deformation at the center of the test piece, the less the deformation in the environment of use at high temperatures, and the better the heat resistance in the presence of alcohol.

(1-6) Methanol resistance test: A test piece of 70 mm × 40 mm × 1.6 mm was cut out from a molded product having a thickness of 1.6 mm prepared by a 70 ° C. immersion test injection molding machine. Next, 150 g of methanol (100%) was put in a 500 ml beaker, the beaker was covered with aluminum foil to prevent the volatilization of methanol, and heated to 70 ° C. in a water bath. Thereafter, when the internal temperature of the beaker reached 70 ° C., the test piece was leaned against the beaker wall such that the side of 40 mm was in contact with the bottom surface of the beaker and 3.5 cm from the bottom surface of the test piece was immersed in methanol. While maintaining the internal temperature of the beaker at 70 ° C., the deformation of the entire test piece including the change in the appearance of the part where the test piece was immersed in methanol and the change in the part not immersed in methanol after 8 hours from there. The occurrence of (softening) was visually evaluated. Evaluation was performed according to the following criteria.
○: No change in appearance and no occurrence of deformation (softening).
X: Appearance change such as whitening and / or deformation (softening) occurred.

(1-7) Average length of component (C) in bending test piece Measured by the method described above.

(1-8) Ultrasonic weldability (tensile strength)
Used resin pieces: Two test pieces for bending test (120 mm × 10 mm × 4 mm) are used.
Used welding tester: SONOPET Σ-1200 manufactured by Seidensha Electronics Co., Ltd.
Welding conditions: welding time 1.0 sec, holding time 1.0 sec, pressurization 1.0 kgf amplitude 21 um.
As shown in FIG. 2, two test pieces were placed so as to overlap each other by 17 mm, and a horn was pressed against a portion 10 mm away from the end of the overlapped upper test piece, and welding was performed under the above conditions. Using the test sample after welding, a normal tensile test was performed with the autograph used in the physical property test, and the tensile strength was measured.

(2-1) Component (A) (olefin resin)
Component (A-1): Homotype polypropylene “Novatech PP FY4” (trade name: manufactured by Nippon Polypro Co., Ltd.) was used.
Component (A-2): Block type polypropylene “Novatech PP BC6C” (trade name: manufactured by Nippon Polypro Co., Ltd.) was used.

(2-2) Component (B) (rubber reinforced resin)
(2-2-1) Component (B-1) (Ethylene-propylene rubber reinforced resin)
A 20-liter stainless steel autoclave equipped with a ribbon-type stirrer blade, auxiliary additive addition device, thermometer, etc., ethylene-propylene rubber (ethylene / propylene / dicyclopentadiene = 63/32/5 (%), Mooney 30 parts of an ethylene-propylene copolymer having a viscosity (ML _{1 + 4} , 100 ° C.) of 33), 45 parts of styrene, 25 parts of acrylonitrile, and 140 parts of toluene are heated to an internal temperature of 75 ° C. Was stirred for 1 hour to obtain a homogeneous solution. Thereafter, 0.45 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. It was. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature.
After cooling the internal temperature to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave and steam distilled. Then, unreacted substances and the solvent were distilled off, and the cylinder temperature was adjusted to 220 ° C. and the degree of vacuum was adjusted to 770 mmHg with an extruder equipped with a 40 mmφ vent, and the volatile matter was substantially degassed and pelletized. The resulting ethylene-propylene rubber reinforced resin has a graft ratio of 60%, an intrinsic viscosity [η] of acetone-soluble content of 0.45 dl / g, and a number average rubber particle size determined by transmission electron micrograph is 0. .57 μm.

(2-2-2) Component (B-2) (hydrogenated conjugated diene rubber-reinforced resin)
A rubber reinforced resin obtained by solution polymerization of methyl methacrylate, styrene, and acrylonitrile in the presence of a hydrogenated styrene-butadiene block copolymer (trade name “Dynalon 4600P”, manufactured by JSR) was used. This rubber reinforced resin has a graft ratio of 45%, a hydrogenated styrene-butadiene block copolymer content of 30%, a methyl methacrylate unit amount of 50%, a styrene unit amount of 10%, and an acrylonitrile unit amount of 10%. The intrinsic viscosity of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) was 0.30 dl / g.

(2-2-3) Component (B-3) (Rubber reinforced resin other than component (B)) (control)
A rubber-reinforced resin (B1-3) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber was prepared. The graft ratio of this rubber reinforced resin is 60%, the intrinsic viscosity of acetone-soluble components (measured in methyl ethyl ketone at 30 ° C.) 0.48 dl / g, polybutadiene rubber content 40%, styrene unit amount 45%, acrylonitrile unit amount 15%.
70 parts of this rubber-reinforced resin (B1-3) and AS resin (B2-3) (styrene-acrylonitrile copolymer having 70% styrene unit amount and 30% acrylonitrile unit amount, intrinsic viscosity of acetone-soluble component (in methyl ethyl ketone, (Measured at 30 ° C.) 0.65 dl / g) and 30 parts were mixed to obtain a rubber-reinforced resin (B-3).

(2-3) Component (C) (convergent glass fiber)
Component (C-1): Aminosilane surface-treated glass fiber “CS03MAA51A” (Owens Corning Japan, average length / average diameter = 3 to 4 mm) converged with a sizing agent comprising a mixture of AS resin and epoxy resin. / 13 μm).
Component (C-2): Aminosilane surface-treated glass fiber “RES03-TP11” (trade name; manufactured by NSG Vetrotex, average length / average diameter = 3 mm / 13 μm) converged with a sizing agent composed of a urethane polymer ).
Component (C-3): Silane surface-treated glass fiber “RES03-TP89Z” (trade name; manufactured by NSG Vetrotex Co., Ltd., average length / average diameter = 3 mm / 13 μm) converged with a sizing agent comprising an acrylic polymer ) (Control).
Component (C-4): Non-fibrous glass flake “REFG-101” (trade name; manufactured by NSG Vetrotex) (control).

(2-4) Component (D) (acid-modified olefin resin)
Component (D-1): Acid-modified propylene-based resin “Yumex 1001” having a maleic acid group and having an acid value of 26 (trade name; manufactured by Sanyo Chemical Industries, Ltd.).
Component (D-2): Acid-modified propylene resin having a maleic acid group and having an acid value of 52 “Yumex 1010” (trade name; manufactured by Sanyo Chemical Industries, Ltd.) (control).

Examples 1-6 and Comparative Examples 1-9
After mixing the above components (A) to (D) with a Henschel mixer at the blending ratio shown in Table 1, they are kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX44, barrel setting temperature 250 ° C.) and pelletized. did. Each test piece for evaluation was shape | molded with the obtained pellet. And it evaluated by the said method using the obtained test piece. The above evaluation results are shown in Table 1.

As can be seen from Table 1, the molding materials of Examples 1 to 6 provide molded products having the intended performance of the present invention.
On the other hand, Comparative Example 1 is an example using a rubber reinforced resin outside the scope of the present invention as the component (B), inferior in gas barrier properties, 50 ° C. heat distortion resistance, 50 ° C. bending maximum stress and The flexural modulus at 50 ° C. is low, and therefore the rigidity at high temperatures is poor. Comparative Example 2 is an example in which glass fibers converged with a sizing agent outside the scope of the present invention are used in place of the component (C) of the present invention, and gas barrier properties, heat-resistant deformation at 50 ° C., at high temperatures The rigidity of is inferior. Comparative Example 3 is an example in which glass flakes are used instead of the component (C) of the present invention, the heat deformation resistance at 50 ° C. and the impact strength are inferior, the bending maximum stress at 50 ° C., and the flexural modulus at 50 ° C. Is low, and therefore the rigidity at high temperatures is poor. Comparative Example 4 is an example using an acid-modified olefin resin in which the acid value of component (D) exceeds the range of the present invention, and is inferior in gas barrier properties and 50 ° C. heat distortion resistance. Comparative Example 5 is an example in which the amount of component (C) used is less than the range of the present invention, and is inferior in ultrasonic weldability, heat-resistant deformation at 50 ° C., and rigidity at high temperatures. Comparative Example 6 is an example in which the amount of component (C) used exceeds the range of the present invention, and the ultrasonic weldability is poor. Comparative Example 7 is an example in which the amount of the component (D) used is less than the range of the present invention, and the gas barrier properties, the heat distortion resistance at 50 ° C., and the rigidity at high temperatures are inferior. Comparative Example 8 is an example in which the amount of component (D) used exceeds the range of the present invention, and the gas barrier properties, the heat distortion resistance at 50 ° C., and the rigidity at high temperatures are poor. Comparative Example 9 is an example in which the amount of component (B) used is less than the range of the present invention, and the impact resistance is poor.

  The alcohol-resistant molding material of the present invention and a molded article such as an alcohol container molded with the same are excellent in chemical resistance with less occurrence of defective phenomena such as whitening, cracking and deformation even when in contact with alcohol. Excellent resistance to permeation, heat resistance in the presence of alcohol, mechanical strength, ultrasonic weldability, and extremely useful for use in conditions that come into contact with alcohol such as fuel containers (including cartridges) for alcohol fuel cells .

It is a schematic longitudinal cross-sectional view which shows the method of the methanol resistance test done in the Example. It is a schematic perspective view which shows the method of the ultrasonic welding test performed in the Example.

Claims (4)

The following component (A) 35-77 mass%, the following component (B) 7-40 mass%, the following component (C) 15-50 mass%, and the following component (D) 0.1-15 mass%. Alcohol-resistant molding material to be contained (however, the total of the components (A), (B), (C) and (D) is 100% by mass).
Component (A): Olefin resin;
Component (B): In the presence of the rubbery polymer (a) comprising the ethylene-α-olefin rubber (a1) and / or the hydrogenated conjugated diene rubber (a2), the vinyl monomer (b) is added. A rubber-reinforced resin comprising a graft copolymer (B1) obtained by polymerization, or a mixture of the graft copolymer (B1) and a (co) polymer (B2) of a vinyl monomer (b);
Component (C): selected from the group consisting of a vinyl monomer copolymer (c1) containing an aromatic vinyl compound and a vinyl cyanide compound, an epoxy resin (c2) and a urethane polymer (c3) Glass fibers converged with at least one sizing agent;
Component (D): An acid-modified olefin resin having an acid value of 5 to 40.   The alcohol-resistant molding material according to claim 1, wherein the component (D) is an olefin resin modified with maleic acid and / or maleic anhydride.   A molded product molded from the alcohol-resistant molding material according to claim 1 or 2.   The molded article according to claim 3, which is an alcohol container.

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