JPH09278955A - Propylene resin composition and its laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a propylene resin composition not only excellent in hot flow stamping moldability, appearance, flexibility, heat resistance, etc., but also recyclable and usable and its laminate. SOLUTION: This propylene resin composition is obtained by dynamically heat-treating a mixture comprising (A) 100 pts.wt. of a propylene-α-olefin copolymer having the ratio of the melt viscosity at 10<1> sec<-1> shear rate to the melt viscosity at 10<2> sec<-1> shear rate of 3.5-8, (B) 5-100 pts.wt. of a rubber-like copolymer, (C) 1-40 pts.wt. of at least one selected from the group consisting of a mineral oil-based softener, a phthalic acid ester-based plasticizer and a silicone oil and (D) 0.005-0.5 pt.wt. of an organic peroxide and has properties of 2-50g/10 minutes melt flow rate, 130-150 deg.C main endothermic peak, 80-100 deg.C main exothermic peak and >=5.0 deg.C half width of the main exothermic peak.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene resin composition which is suitable for use as a skin material for industrial parts and the like, which has excellent hot flow stapping properties, impact resistance, scratch resistance and heat cycle properties, and It relates to the laminated body.

[0002]

2. Description of the Related Art Conventionally, stamping molding has been used as a molding method for skin materials for industrial parts including interior materials in the field of automobiles. The molding method is a method of reheating a sheet material once solidified and shaping it, and there is a lot of waste in terms of energy or a problem in terms of cost. In recent years, hot flow stamping molding, which directly molds and shapes a molten resin, has been developed and attracts attention. Although a soft vinyl chloride resin has been used as a skin material in the molding, a material substitute is demanded due to bleeding out by a plasticizer or environmental problems.

As a method for solving this problem, a method using an olefinic thermoplastic elastomer has been proposed. For example, a resin composition comprising ethylene-propylene rubber, an ethylene-propylene random copolymer and peroxide (JP-A-5-331326), an oil-extended olefin obtained by adding a mineral oil-based softening agent to an olefin copolymer rubber. An elastomer obtained by partially cross-linking a mixture of olefin polymers (Japanese Patent Laid-Open No. 6-57065),
Composition of poly-1-butene resin and partially cross-linked thermoplastic elastomer (JP-A-6-256538, JP-A-6-256538)
-287323, JP-A-6-287377, JP-A-7-179624).

[0004]

However, all of these methods are not suitable for hot flow stamping formability,
There is a problem that flexibility and recyclability are poor.
The present invention has been made in view of such circumstances, propylene which is excellent in hot flow stapling characteristics, and is preferably used as a skin material for industrial parts having good impact resistance, scratch resistance and heat cycle property. It is intended to provide a resin composition and a laminate thereof.

[0005]

As a result of intensive studies, the present inventors have found that the above object can be achieved by a specific propylene-α-olefin block copolymer, and based on this finding, the present invention The invention was completed.

That is, the present invention (A) has a shear rate of 10 ¹ sec measured at 170 ° C. by the slit die method.
^-1 melt viscosity (η ₁ ) and shear rate 10 ² sec ^-1
The ratio (η ₁ / η ₂ ) to the melt viscosity (η ₂ ) at 3.
Propylene-α-olefin copolymer of 5 to 8 1
00 parts by weight, (B) rubber-like polymer 5 to 100 parts by weight, (C) at least one plasticizer selected from the group consisting of mineral oil-based softeners, phthalate ester-based plasticizers and silicone oils 1 to 40 parts by weight and a mixture of (D) 0.005 to 0.5 parts by weight of an organic peroxide are obtained by dynamically heat-treating, and (a) below.
The invention provides a propylene resin composition having properties of (e) to (e). (A) Melt flow rate 2 to 50 g / 10 minutes (b) Main endothermic peak temperature 130 to 150 ° C (c) Main exothermic peak temperature 80 to 100 ° C (d) Half width of main exothermic peak 5.0 ° C or more (e ) Main heat energy 30 J / g or less

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Propylene-α-olefin copolymer (hereinafter referred to as "BPP") in the present invention
Is a polypropylene block and propylene and other α-
It is a block copolymer composed of a copolymer block with an olefin. Specific examples of other α-olefins include ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-
Dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane and the like can be mentioned. These α-olefins may be used alone or in combination of two or more. The BPP of the present invention has a temperature of 17 by the slit die method.
0 melt viscosity at a shear rate of 10 ¹ sec ^-1 measured at ° C. (eta ₁₎ the ratio of the melt viscosity (eta ₂₎ at a shear rate of _{^{10 2 sec -1 (η 1 /}} η 2) is 3.5 to Must be 8.

Here, the slit die method is CDHan; Rh.
eology in Polymer Processing, Academic, New York (197
6) and JL White; Principles of Polymer Engineerin
g Rheology, John Wiley, New York (1990), which is a method for measuring melt viscosity using a slit die having a width of 20 mm, a height of 1.5 mm and a length of 60 mm. A viscometer according to the method is commercially available, and examples thereof include Laboplast mill D20-2-type (manufactured by Toyo Seiki Seisakusho).

Η ₁ / η ₂ is preferably 4.0 to 7.5,
Particularly, 4.5 to 7 is preferable. When the melt viscosity ratio is less than 3.5, the drawdown is large and the press formability is poor. On the other hand, when it exceeds 8, the press formability is deteriorated, which is not preferable. The BPP of the present invention comprises a polypropylene block,
It is preferably composed of a copolymer block of propylene and another α-olefin having 12 or less carbon atoms, and the proportion of the copolymer block is preferably 30 to 70% by weight, and particularly preferably 40 to 65% by weight. is there.

Further, as the BPP having good press formability, those having the following properties (i) and (ii) are preferable. (I) Para-xylene insoluble matter 25 at a temperature of 25 ° C.
65 wt% (ii) Paraxylene-soluble matter at a temperature of 25 ° C is
(A) The average propylene content (FP) obtained using the two-site model is 20 to 80 mol%, and (b) the copolymer (P _H ) formed at the active sites for preferentially polymerizing propylene in the two-site model. Has a propylene content (P _P ) of 65
˜90 mol%, and the ratio (P _f1 ) of (C) P _H in the copolymer is 0.40 to 0.90.

(I) Paraxylene-insoluble matter means that after BPP is dissolved in para-xylene at a temperature of 130 ° C. in an amount of about 1% by weight,
It is an insoluble component that precipitates when cooled to 25 ° C, and in the present invention, 30 to 60% by weight is particularly preferable. Also,
(Ii) The para-xylene soluble component is a component dissolved by the above-mentioned operation, and it is preferable that the properties obtained by using the two-site model are within the above range.

Here, 2 of propylene-α-olefin
The site model will be described by taking a propylene-ethylene copolymer as an example. An example of a nuclear magnetic resonance ( ¹³ C-NMR) spectrum of isotope carbon of a propylene-ethylene copolymer is shown in FIG. The spectra are (1) to (10) due to the difference in the chain distribution (the arrangement of ethylene and propylene).
10 appear. The name of this chain is Ca
rman.CJ et al; Macromolecues, Vol.10, p536-544 (1977)
2 and the name is shown in FIG. Such a chain can be expressed as a reaction probability (P) assuming a reaction mechanism of copolymerization, and the relative intensity of each peak of (1) to (10) is P when the overall peak intensity is 1. Can be expressed as a stochastic equation based on Bernoulli statistics.

For example, in the case of (1) Sαα, if the propylene unit is the symbol p and the ethylene unit is the symbol e, the possible chains are [pppp], [pppe], and [epp].
e], and these are referred to as reaction probabilities (P), respectively.
Express and add. The remaining peaks (2) to (10) can be obtained by formulating equations in the same manner, and optimizing P so that the peak intensity actually measured is closest to these 10 equations. .

The two-site model is a model that assumes this reaction mechanism. HNCHENG; Journal of Applied Polym
er Science, Vol. 35 p1639-1650 (1988). That is, in the model of copolymerizing propylene and ethylene using a catalyst, the copolymer produced in the active sites of polymerization preferentially propylene and propylene content of _{(P H) (P P)} , preferentially polymerizing ethylene Assuming that the propylene content (P ′ _P ) of the copolymer formed at the active sites is 2 and the ratio of P _H in the copolymer (P _f1 ) is a parameter, it is shown in Table 1 below. A stochastic equation is obtained.

[0015]

[Table 1]

Therefore, the relative intensity of the ¹³ C-NMR spectrum and the probability equation shown in Table 1 are matched so that P
It is obtained by optimizing the three parameters of _P , P ′ _P and P _f1 .

The (a) average propylene content (FP) of the BPP of the present invention is determined by the following equation using the above three parameters. _{FP = P P × P f1 ×} P 'P × (1-P f1) ( mol%) FP obtained by the above formula is preferably 30 to 70 mol%. In addition, (b) P _P of the above parameters is 70-
85 mol%, and (c) P _f1 is preferably 0.48 to 0.82.

The BPP polymerization of the present invention is carried out in the presence of an inert hydrocarbon such as hexane, heptane, kerosene or a liquefied α-olefin solvent such as propylene in a slurry method,
There is a vapor phase polymerization method in the absence of a solvent, and any method may be used. As the reactor, those usually used in the technical field can be appropriately used, and examples thereof include a stirred tank reactor, a fluidized bed reactor, a circulation reactor, and the like. It can be manufactured by either a batch method or a batch method. The reaction conditions are room temperature to 130 ° C., preferably 50 to 90 ° C., and pressure of ^{2 to} 50 kg / cm ² .

As a specific method, a known multistage polymerization method can be used. That is, a method of polymerizing propylene and / or a propylene-α-olefin copolymer in a first-step reaction and then copolymerizing propylene and an α-olefin in a second-step reaction, which is disclosed in JP-A-3-9774.
No. 7, JP-A-3-205439, JP-A-4-
No. 153203, JP-A-4-261423 and JP-A-5-93024. The MFR of BPP obtained by the above method is generally 2 g / 10.
Minutes or less.

The rubbery polymer (B) in the present invention is not particularly limited, and examples thereof include natural rubber (NR);
Butadiene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), styrene-butadiene rubber (SBR), isobutene-isoprene rubber (IIR),
Acrylonitrile-butadiene rubber (NBR), ethylene-propylene copolymer rubber (EPR), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), propylene-butene rubber, butyl rubber, silicone rubber, fluorosilicone rubber, nitrile rubber, epichlorohydrin rubber Synthetic rubber such as styrene / isoprene-styrene block copolymer (SIS), styrene-ethylene / isoprene-styrene block copolymer (SEPS), styrene / butadiene-styrene block copolymer (SB)
S), styrene-ethylene / butadiene-styrene block copolymer (SEBS) and other styrene-based elastomers, olefin-based elastomers, ester-based elastomers and other various thermoplastic elastomers.

Furthermore, polybutene, which is a low molecular weight rubber,
Artic polypropylene (APP); liquid BR,
Liquid rubbers such as liquid IR and liquid CR, and chlorinated polyolefins such as chlorinated polyethylene and chlorinated ethylene-propylene copolymer rubber; chlorosulfonated polyethylene and the like are also included. Among these, EPR and E
PDM, hydrogenated SBR, SEPS, etc. are preferably used. These may be used alone or as a mixture of two or more.

In the present invention, the blending ratio of the component (B) to 100 parts by weight of BPP is 5 to 100 parts by weight, preferably 10 to 90 parts by weight, and more preferably 15 to 85 parts by weight.
Parts by weight are preferred. If the blending ratio of the component (B) is less than 5 parts by weight, the flexibility is poor. On the other hand, if it exceeds 100 parts by weight, the mechanical strength is lowered, which is not preferable.

The (C) plasticizer in the present invention is at least one selected from the group consisting of mineral oil softeners, phthalate ester plasticizers and silicone oils. The mineral oil-based softening agent is a petroleum fraction having a high boiling point, and has various types such as paraffin-based, naphthene-based, and aromatic-based, and is used as a softening agent during rubber processing. Of these, paraffinic softeners are preferable.

The phthalate ester type plasticizer is used as a plasticizer for vinyl chloride resin, and includes, for example, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate and di-phthalate. n-octyl, di-2-ethylhexyl phthalate,
Diisooctyl phthalate, di-n-octyl phthalate,
Examples thereof include dinolyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, butyllauryl phthalate, and methyloleyl phthalate. Of these, dimethyl phthalate, diethyl phthalate and diisobutyl phthalate are preferred.

Silicone oil is a fluid oily substance mainly composed of linear diorganopolysiloxane, and is used as an additive for hydraulic oils, mold release agents, defoamers, paints, cosmetics and the like. It is a thing. As a specific example,
Dimethyl polysiloxane, monomethyl polysiloxane,
Methylphenyl polysiloxane, alkyl modified silicone, amino modified silicone, epoxy modified silicone,
Examples thereof include carboxyl modified silicone, mercapto modified silicone, alkyl higher alcohol modified silicone, alcohol modified silicone, chloroalkyl modified silicone, polyether modified silicone, and fluorine modified silicone. Of these, dimethylpolysiloxane, monomethylpolysiloxane and methylphenylpolysiloxane are preferable. These silicone oils may be used alone or in combination of two or more.

In the present invention, the compounding ratio of the component (C) to 100 parts by weight of BPP is 1 to 40 parts by weight, preferably 2 to 35 parts by weight, and particularly 3 to 3 parts by weight.
0 parts by weight is preferred. When the composition ratio of the component (C) is less than 1 part by weight, flexibility and press moldability are poor. Meanwhile, 4
If it exceeds 0 parts by weight, it may cause bleed-out, which is not preferable.

The organic peroxide (D) in the present invention is not particularly limited, but the decomposition rate of BPP at the melting point temperature is more than 1 second in half-life and 30
It is preferable that the decomposition rate at 0 ° C. is 10 minutes or less.
Specifically, t-butyl hydroperoxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, benzoyl peroxide, methyl isobutyl ketone peroxide, t-butyl perbenzoate, diisopropyl peroxide. Examples thereof include oxydicarbonate and vinyltris (t-butylperoxy) silane. The blending ratio of these organic peroxides is 0.005 to 0.5 part by weight, preferably 0.01 to 0.45 part by weight, particularly 0.02 to 0.40 part by weight, relative to 100 parts by weight of BPP. Is preferred. If the blending ratio is less than 0.005 part by weight, the press formability is poor. on the other hand,
If it exceeds 0.5 parts by weight, the mechanical strength is lowered, which is not preferable.

The resin composition of the present invention is obtained by mixing the above components and dynamically heat treating them. As the dynamic heat treatment method, a conventionally known melt kneading method can be mentioned. For example, it may be kneaded using a mixer such as an open roll, a Banbury mixer, a kneader, or an extruder. The temperature during kneading is generally 170 to 280 ° C,
190-260 degreeC is preferable.

The resin composition of the present invention thus obtained is
It is necessary to have the following properties (a) to (e). (A) Melt flow rate 2 to 50 g / 10 minutes (b) Main endothermic peak temperature 130 to 150 ° C (c) Main exothermic peak temperature 80 to 100 ° C (d) Half width of main exothermic peak 5.0 ° C or more (e) ) Main heat energy 30 J / g or less

First, (a) the melt flow rate (hereinafter referred to as "MFR") is a value measured in accordance with JIS K7210 at a temperature of 230 ° C. and a load of 2.16 kg, which is 3 to 45 g / 10. Minutes are preferred, especially 4-40 g / 10 minutes. MFR is 2g / 10
If it is less than minutes, the hot flow stamping formability is poor. On the other hand, when it exceeds 50 g / 10 minutes, it becomes difficult to obtain a thick molded product, which is not preferable.

(B) Main endothermic peak temperature (hereinafter "Tmp")
Is a differential scanning calorimeter (hereinafter referred to as "DSC")
It is the peak temperature when the melting curve is measured using.
Tmp is preferably 132 to 148 ° C., particularly 135 to 1
45 ° C is preferred. If Tmp is less than 130 ° C, it is difficult to increase the thickness of the molded product. On the other hand, if the temperature exceeds 150 ° C, the hot flow stamping moldability is deteriorated, which is not preferable.

(C) The main exothermic peak temperature is the peak temperature (hereinafter referred to as "Tc" when a crystallization curve is measured by DSC.
p ”). Tcp is preferably 133 to 148 ° C, and particularly preferably 135 to 145 ° C. Tcp is 8
If it is less than 0 ° C, the molding cycle and the heat cycle property during hot flow stamping molding are poor. On the other hand, 100 ° C
If it exceeds the range, the impact resistance is deteriorated, which is not preferable.

(D) The full width at half maximum of the main exothermic peak is the temperature width at 50% height of the peak, and is preferably 6 ° C. or higher, particularly preferably 7 ° C. or higher. When the full width at half maximum is less than 5%, impact resistance and flexibility are poor. (E) The main exothermic energy is obtained from the exothermic peak area of the DSC crystallization curve. The energy is preferably 28 J / g or less, and particularly preferably 25 J / g or less. If the energy exceeds 30 J / g, the impact resistance becomes poor, which is not preferable.

The above DSC curve was measured under the following conditions.
That is, the crystallization curve is obtained by once raising the temperature to 230 ° C., maintaining the temperature for 5 minutes, and then cooling to −30 ° C. at a temperature decreasing rate of 20 ° C./min. Next, after maintaining at −30 ° C. for 5 minutes, the temperature is raised to 230 ° C. at a temperature rising rate of 20 ° C./minute to obtain a melting curve.

For the resin composition of the present invention, other additives conventionally used in the art (for example, antioxidants, weather resistance stabilizers, antistatic agents, lubricants, antiblocking agents, antifog agents, Dyes, pigments, oils, waxes, fillers, etc.) and other thermoplastic resins can be added in appropriate amounts within the range not impairing the object of the present invention.

Examples of such additives include 2,5-di-t-butylhydroquinone as an antioxidant and 2,2
6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2-methylene-bis- (4-methyl-6-t-butylphenol), octadecyl-3 -(3 ', 5'-di-t-butyl-1'-hydroxyphenyl) propionate, 4,
4'-thiobis- (6-butylphenol), UV absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy-4 -Octoxybenzophenone, dimethyl phthalate, diethyl phthalate as plasticizer, wax, liquid paraffin, phosphoric acid ester, pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide as antistatic agent, Carbon wax, ethylene bis stearamide, butyl stearate, etc. as a lubricant, carbon black, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc. as a colorant, glass fiber, asbestos, mai as a filler. , Wollastonite, calcium silicate, aluminum silicate, calcium carbonate, also many other high molecular compounds may be blended to the extent that effect can not be inhibited in the present invention.

The molding method using the resin composition of the present invention as a skin material for industrial parts includes the following methods, and is not particularly limited, but the hot flow stamping molding method (5) is particularly preferable. Used. (1) Multi-layer co-extrusion molding (2) Multi-layer injection molding and insert molding (3) After being formed into a sheet by the T-die molding method or the calendar molding method, the laminate laminated on the base material is vacuum-formed or stamped-molded (4) Hot-flow stamping molding in which foam is further laminated on the laminated body of (3), and then vacuum molding or stamping molding is performed (5) melt extrusion onto a base material and immediate pressing

As the hot flow stamping molding method, in addition to this, a method of supplying a skin material layer with an injection molding machine (Japanese Patent Laid-Open No. 7-81410, etc.) or a method of forming a foam layer at a temperature below the foaming temperature together with the skin material layer in a mold And a method of extrusion-feeding and molding.

The industrial skin material obtained by molding the resin composition of the present invention may be used as an instrument panel,
Console box, door trim, seat shield, rear panel, steering wheel cover, automobile interior parts such as ceiling materials, TV, radio, video, air conditioner,
Coolers, coffee makers, jars, telephones, copiers, facsimiles, and other electrical / electronic devices, sports equipment, furniture, desks, wall decorations, rugs, and other construction-related items, notebooks, stationery such as albums, camera bags, attache cases, etc. Carrying bags and the like.

[0040]

The present invention will be described in more detail with reference to the following examples. The methods for measuring physical properties are shown below. 1) Melt viscosity Laboplast mill D20-20 type manufactured by Tokyo Seiki Seisaku-sho, Ltd. was used. 2) Para-xylene insoluble matter and soluble matter The polymer was once dissolved in para-xylene at a temperature of 130 ° C to a concentration of about 1% by weight, then cooled to a temperature of 25 ° C, and the precipitated matter was taken as the para-xylene insoluble matter, Those that did not precipitate were taken as the para-xylene solubles, and the weight ratio was determined. The para-xylene solubles were used for the next measurement of the ¹³ C-NMR spectrum.

3) ¹³ C-NMR spectrum analyzer: JNM-GSX400 manufactured by JEOL Ltd. Measurement mode: Proton decoupling method Pulse width: 8.0 μsec Pulse repetition time: 5.0 μsec Accumulation frequency: 20000 times Solvent: Mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene (75/25% by volume) Internal standard: Hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C

4) DSC curve device: DSC7 type manufactured by PERKIN-ELMER Sample weight: about 3 to 5 mg 5) Measured using a melt indexer manufactured by Takara in accordance with MFR JIS K7210. 6) Feeling test The sheet surface was evaluated by the tentacles in the following four stages. A: The surface is soft and the surface is dry B: The surface is soft and the surface is tight C: The softness is slightly inferior D: The surface is soft and dry Are

7) Friction resistance test The friction coefficient between the sheet and the JIS No. 8 cotton cloth was measured using a friction tester manufactured by Tester Sangyo Co., Ltd. under a load of 300 g and a test speed of 150.
It was measured under the condition of mm / min. 8) Scratch resistance The surface of the sheet was expressed by the load when scratched using a Taber type scratch tester (manufactured by Toyo Seiki Seisakusho). 9) Fluidity of Melt Film The fluidity of the film at the die exit during coextrusion molding was visually evaluated in the following three stages. ○ ・ ・ ・ ・ Flows with a uniform film thickness without curling △ ・ ・ ・ ・ Curses slightly and flows with an uneven film thickness × ・ ・ ・ ・ ・ ・ Curses are significant and the film thickness becomes uneven

10) Flexibility The hardness of the laminated body was measured using a JIS C type hardness meter. 11) Peel strength A test piece having a width of 25 mm and a length of 200 mm was pulled at a pulling speed of 20 using a tensile tester (RTA100 type manufactured by ORITEC).
The 180 ° peel strength was measured under the condition of 0 mm / min. 12) Heat resistance A test piece having a size of 100 × 100 mm was exposed in an oven at a temperature of 100 ° C. for 400 hours, and the appearance was visually evaluated in the following three stages. ○ ・ ・ ・ ・ No deformation or color change △ ・ ・ ・ ・ No deformation, but gloss increased × ・ ・ ・ ・ Deformation and gloss increased 13) Moisture aging resistance Test piece of size 100 × 100 mm Was exposed to a thermo-hygrostat at a temperature of 50 ° C. and a humidity of 95% for 250 hours, and the appearance was visually evaluated in the following three grades. The film surface was visually evaluated in the following three grades. ○ ・ ・ ・ ・ No deformation or color change △ ・ ・ ・ ・ No deformation, but glossiness increased × ・ ・ ・ ・ Deformation and gloss increased 14) Heat shrinkage rate 100 × 100 mm test piece Was exposed in an oven at a temperature of 100 ° C. for 200 hours and then cooled to room temperature, and the shrinkage ratio was measured and expressed in%.

As the component (A), BPP1 to BPP7 shown in Table 2 (where BPP6 and 7 are for comparative examples) obtained by polymerization according to a well-known multistage polymerization method and homopolypropylene for comparative examples (hereinafter "PP") are used. Was used).

[0046]

[Table 2]

The following compounds were used as the component (B). EP: EPR ("EP941P" manufactured by Japan Synthetic Rubber Co., Ltd.) ST: Styrene-isoprene copolymer water additive ("Septon 4055" manufactured by Kuraray Co., Ltd.) The following compounds were used as the component (C). OL1: Hydrogenated process oil (“PW38 manufactured by Idemitsu Kosan Co., Ltd.
0 ") OL2: dibutyl phthalate (manufactured by Kurogane Kasei) OL3: dimethyl polysiloxane (" SH200 "manufactured by Toray Silicone Co., Ltd.) Further, as the component (D), 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane was used.

Examples 1 to 8 and Comparative Examples 1 to 4 [Kneading treatment] Each component whose type and blending amount are shown in Table 3 and pentaerythrityl-tetrakis [3- (3,5-di) as a stabilizer. 0.1 part by weight of -t-butyl-4-hydroxyphenyl)] propionate, 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of calcium stearate were added. , Kawada Manufacturing Super Mixer (SMV
20 type) and mixed into pellets using a twin-screw extruder (KTX37 type) manufactured by Kobe Steel. The MFR of each obtained pellet was measured.

[Sheet molding] Using a hot flow stamping molding machine (Model FSM450 manufactured by Takahashi Industry Co., Ltd.), the die temperature is 220 ° C., the die temperature is 70 ° C., and the die clamping pressure is 200.
Under the condition of tons, a die with a grain (600 mm x 800 mm
X depth of 5 mm), each of the above pellets was melted again using a twin-screw extruder, and hot-flow stamping molded on a polypropylene substrate. Each of the obtained sheets was evaluated for touch test, friction resistance test and scratch resistance. Table 3 shows the above results.

[0050]

[Table 3]

Examples 9 to 12, Comparative Examples 5 and 6 100 parts by weight of ethylene-maleic anhydride-methyl methacrylate terpolymer (maleic anhydride: 2.5% by weight, methyl methacrylate: 18.2% by weight) , 5 parts by weight of a foaming agent (4,4′-oxybisbenzenesulfonylhydrazide), 1.5 parts by weight of azodicarboxylic acid amide, and pentaerythrityl-tetrakis [3 as a stabilizer.
0.1 part by weight of-(3,5-di-t-butyl-4-hydroxyphenyl)] propionate, tris (2,4-
0.1 part by weight of di-t-butylphenyl) phosphite was pelletized in the same manner as above. The obtained pellets and the pellets were coextruded using a coextrusion T-die molding machine (manufactured by Yoshii Iron Works Co., Ltd.) at a temperature (130 ° C.) at which the foaming agent did not foam. With respect to each of the obtained laminates, the fluidity, flexibility, peel strength, heat resistance, moisture aging resistance and heat shrinkage of the melt film were evaluated. Table 4 shows the above results.

[0052]

[Table 4]

[0053]

The propylene resin composition of the present invention and the laminate thereof have excellent hot flow stamping moldability,
Not only good appearance, flexibility, heat resistance, etc., but also recyclable, it is useful as a skin material and a laminate for automobiles, home appliances, daily necessities and the like.

[Brief description of drawings]

FIG. 1 is an example of a nuclear magnetic resonance spectrum of isotope carbon of an ethylene-propylene copolymer.

FIG. 2 is a view showing names of carbons derived from a chain distribution in a polyolefin.

FIG. 3 is an example of a DSC melting temperature curve of the propylene resin composition of the present invention.

FIG. 4 is an example of a DSC crystallization temperature curve of the propylene resin composition of the present invention.

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Claims (7)

[Claims] 1. A temperature of 170 according to (A) slit die method.
The ratio of the melt viscosity (eta ₂₎ ° C. melt viscosity at a shear rate of 10 ¹ sec ^-1 as measured by the (eta ₁₎ at a shear rate of _{^{10 2 sec -1 (η 1 /}} η 2) is 3.5-8 Selected from the group consisting of 100 parts by weight of propylene-α-olefin copolymer, (B) 5 to 100 parts by weight of rubbery polymer, (C) mineral oil-based softening agent, phthalate ester-based plasticizer and silicone oil. Obtained by dynamically heat treating a mixture of at least one plasticizer of 1 to 40 parts by weight and (D) an organic peroxide of 0.005 to 0.5 parts by weight, and (a)
A propylene resin composition having the properties of (e). (A) Melt flow rate 2 to 50 g / 10 minutes (b) Main endothermic peak temperature 130 to 150 ° C (c) Main exothermic peak temperature 80 to 100 ° C (d) Half width of main exothermic peak 5.0 ° C or more 2. The component (A) comprises a polypropylene block and a copolymer block of propylene and another α-olefin having 12 or less carbon atoms, and the proportion of the copolymer block is 30 to 70% by weight. The propylene resin composition according to claim 1. 3. The propylene resin composition according to claim 1, wherein the component (A) has the following properties (i) and (ii). (I) Para-xylene insoluble matter 25 at a temperature of 25 ° C.
65 wt% (ii) Paraxylene-soluble matter at a temperature of 25 ° C is
(A) The average propylene content (FP) obtained using the two-site model is 20 to 80 mol%, and (b) the copolymer (P _H ) formed at the active sites for preferentially polymerizing propylene in the two-site model. Has a propylene content (P _P ) of 65
˜90 mol%, and the ratio (P _f1 ) of (C) P _H in the copolymer is 0.40 to 0.90. 4. The propylene resin composition according to claim 1, wherein the component (B) is an ethylene-propylene copolymer elastomer and / or a styrene elastomer. 5. A skin material for industrial parts, which is obtained by molding the propylene resin composition according to any one of claims 1 to 4. 6. The skin material according to claim 5, wherein the industrial parts are interior parts for automobiles. 7. A laminate obtained by laminating a foam on the skin material for industrial parts according to claim 5.