JP4379593B2 - Resin laminate - Google Patents

Description

  The present invention relates to a resin laminate, and more particularly, to a resin laminate having a surface layer that is highly glossy and excellent in flexibility and scratch resistance.

  For example, automobile exterior moldings such as roof moldings are required to have design characteristics, particularly high glossiness and scratch resistance similar to metals, in addition to weather resistance and heat resistance.

  Conventionally, a soft vinyl chloride resin has been mainly used as a molding material as described above, but in recent years, there has been an increasing demand for conversion to an olefin-based resin material due to problems such as weight reduction.

  However, olefin-based resin materials, particularly soft materials such as olefin-based elastomers and styrene-based elastomers, have a drawback that they are more easily scratched than soft vinyl chloride resins, and the scratches are more noticeable when the surface gloss is increased.

  Therefore, it has been proposed to use a high-hardness resin composition such as an ethylene- (meth) acrylic acid copolymer, an ionomer resin, or a highly crystalline polypropylene resin composition on the design surface (for example, Patent Documents 1 and 2). .

  However, parts that require bending such as roof molding need flexibility for bending, cannot be coated with hard resin, and are difficult to gloss. On the other hand, when a cross-linked olefin-based thermoplastic elastomer (TPO) is used, there is a drawback in that an over-density gel locally generated from the manufacturing method causes a rough appearance on the surface.

Utility Model No. 2597587 JP-A-11-208273

  This invention is made | formed in view of the said situation, The objective is to provide the resin laminated body which has the surface layer which was highly glossy and excellent in a softness | flexibility and damage resistance.

  As a result of intensive studies, the present inventors easily achieved the above object by using a specific propylene copolymer selected from various known propylene polymers as the surface layer material. As a result, the present invention was completed.

That is, the gist of the present invention is a resin laminate obtained by the surface layer and formed Ri and coextruded from formed on the design surface side of the resin substrate and the resin substrate, the resin substrate, the surface layer It is made of one or more materials selected from the group consisting of olefin-based resins, olefin-based elastomers, and styrene-based elastomers, and the surface layer is made of material (I) or material (II). The resin component of I) is composed of a propylene copolymer that satisfies the following conditions (1) to (5) , and the resin component of the material (II) is the above propylene copolymer and other polypropylene resins. and the proportion of propylene copolymer to the total amount of both made to have Ri der least 50 wt%, and the surface layer of the D hardness of above Ru 40-60 der, for automotive exterior parts, characterized in that Resin lamination It resides in.

(1) A copolymer of propylene and another α-olefin having 2 to 8 carbon atoms.
(2) The proportion of the portion soluble in xylene at room temperature in the copolymer is 10 to 60% by weight.
(3) The content of α-olefin other than propylene in the portion soluble in xylene at room temperature is 5 to 30% by weight.
(4) The melting point peak temperature is 160 ° C. or higher.
(5) Including at least two or more stages of polymerization, after obtaining a propylene homopolymer in the first stage, propylene and ethylene having essential components of propylene and ethylene in the second and subsequent stages Obtained by a production method for obtaining a copolymer with an α-olefin.

  ADVANTAGE OF THE INVENTION According to this invention, the resin laminated body which has a surface layer excellent in a softness and the softness | flexibility and damage resistance which is used suitably especially for the automotive molding use is provided.

  Hereinafter, the present invention will be described in detail. The resin laminate of the present invention comprises a resin substrate and a surface layer formed on the design surface side of the resin substrate.

  In the present invention, the resin substrate is composed of one or more materials selected from the group of olefin resins, olefin elastomers, and styrene elastomers arranged along the surface layer. A resin with hardness or rigidity is selected.

  Examples of the olefin-based resin include polyethylene, polypropylene, and copolymers thereof. From the viewpoint of heat resistance, moldability, and the like, a polypropylene resin or a copolymer thereof is preferable, and may be necessary depending on applications and parts. Select one that is rigid or fluid.

  Examples of the olefin elastomer include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), ethylene-1-butene-nonconjugated diene copolymer rubber, propylene-1-butene. -A mixture of an olefin-based resin such as polypropylene and polyethylene and an elastic copolymer mainly composed of olefin such as non-conjugated diene copolymer rubber.

  Examples of the styrene elastomer include a mixture of an elastic polymer mainly composed of styrene such as a styrene block copolymer and an olefin resin such as polypropylene and polyethylene.

  Elastomers as described above are commercially available. For example, in the case of olefin-based elastomers, Mitsubishi Chemical Corporation “Thermo Run”, Mitsui Chemicals Inc. “Milastomer”, AES Japan Inc. “Santoprene”, Sumitomo Chemical Industries “Sumitomo TPE”, Examples of styrene elastomers include Mitsubishi Chemical's “Rabalon” and Apco's “Sumiflex”. These elastomers may be selected from those having the required hardness and fluidity depending on the application and site.

  The above-mentioned olefin resin, olefin elastomer, and styrene elastomer may be blended with an inorganic filler for the purpose of improving rigidity, thermal expansion coefficient, and moldability. Examples of the inorganic filler include glass fiber, talc, mica, calcium carbonate, clay, potassium titanate whisker, silica and the like, and these may be used alone or in combination.

  The surface layer in this invention says the layer formed in the design surface side of said resin base | substrate. As an example of the case where the resin substrate arranged along the surface layer is made of a plurality of materials, the hard portion and the soft portion may coexist. In such a case, the surface layer is applied to both the hard portion and the soft portion. Is done.

  Said surface layer is comprised with material (I) or material (II), and the resin component of material (I) consists of the propylene-type copolymer which satisfies the conditions of the following (1)-(3), The resin component of material (II) consists of said propylene-type copolymer and another polypropylene resin, and the ratio of the propylene-type copolymer with respect to the total amount of both is 50 weight% or more.

(1) A copolymer of propylene and another α-olefin having 2 to 8 carbon atoms.
(2) The proportion of the portion soluble in xylene at room temperature in the copolymer is 10 to 60% by weight.
(3) The content of α-olefin other than propylene in the portion soluble in xylene at room temperature is 5 to 30% by weight.

  Examples of the other α-olefin in the above (1) include ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. In particular, ethylene is preferable.

  The proportion of the portion soluble in xylene at room temperature in the above (2) (hereinafter referred to as “CXS”) is preferably 20 to 50% by weight, and the α-olefin content in the above (3) (hereinafter referred to as “αT”). Is preferably 10 to 20% by weight.

  When “CXS” is less than 10% by weight, the flexibility is inferior, whereas when it exceeds 60% by weight, the scratch resistance is inferior. Further, when “αT” is less than 5% by weight, the flexibility is inferior, whereas when it exceeds 30% by weight, the scratch resistance is inferior.

  The propylene copolymer preferably has a melting point peak temperature of 160 ° C. or higher. When the melting point peak temperature is less than 160 ° C., the low molecular weight component bleeds out easily from the resin substrate.

  The method for producing the propylene-based copolymer is not particularly limited. For example, the methods described in JP-A No. 2001-226435 and JP-A No. 2001-172454 can be employed, but preferred production thereof is possible. The method includes at least two stages of polymerization steps, and after obtaining a propylene homopolymer in the first stage, a copolymer of propylene and another α-olefin having 2 to 8 carbon atoms is obtained in the second stage and thereafter. It is a manufacturing method, and the content is explained in full detail below.

  The catalyst used for the above sequential polymerization is not particularly limited, but a catalyst comprising an organoaluminum compound and a solid component essentially comprising a titanium atom, a magnesium atom, a halogen atom and an electron donating compound is preferable. Such catalysts are already known.

Examples of the organoaluminum compounds represented by the general formula ^{_{R 1 m AlX (3-m}} ) ( In the formula, ^{R 1} is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen atoms, m is 1 to 3 Compounds such as trialkylaluminums such as trimethylaluminum and triethylaluminum, dialkylaluminum halides such as dimethylaluminum chloride and diethylaluminum chloride, and alkylaluminums such as methylaluminum sesquichloride and ethylaluminum sesquichloride. Examples thereof include alkylaluminum dihalides such as sesquihalide, methylaluminum dichloride and ethylaluminum dichloride, and alkylaluminum hydrides such as diethylaluminum hydride.

In the above solid component, the titanium compound serving as a source of titanium atoms, the general formula _{^{Ti (OR 2) (4-}} n) X n ( wherein, ^{R 2} is a hydrocarbon residue having 1 to 10 carbon atoms, X represents a halogen atom, and n is a number of 0 to 4.), and titanium tetrachloride, tetraethoxy titanium, and tetrabutoxy titanium are particularly preferable.

  In the solid component, examples of the magnesium compound that serves as a supply source of magnesium atoms include dialkyl magnesium, magnesium dihalide, dialkoxy magnesium, alkoxy magnesium halide, and the like, and magnesium dihalide is particularly preferable.

  In the above-mentioned solid component, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and chlorine is particularly preferable. These are usually supplied from the titanium compound or magnesium compound described above. It may be supplied from other halogen sources such as silicon halide and tungsten halide.

In the solid component, the electron-donating compound is typically an oxygen-containing compound and a nitrogen-containing compound. Examples of oxygen-containing compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acids or inorganic acids and derivatives thereof, and nitrogen-containing compounds include ammonia, amines, nitriles, Isocyanates and the like. Among these, inorganic acid esters, organic acid esters, organic acid halides are preferred, silicic acid esters, phthalic acid esters, cellosolve acetate ester, more preferably phthalic acid halide of the general formula _{^{R 3 R 4 (3-p}} ) Si ( OR ⁵ ) An organosilicon compound represented by _p is particularly preferred.

In the above general formula, R ³ is a branched aliphatic hydrocarbon residue having 3 to 20 (preferably 4 to 10) carbon atoms, or cyclic aliphatic carbonization having 5 to 20 (preferably 6 to 10) carbon atoms. R ⁴ represents a branched or straight-chain aliphatic hydrocarbon residue having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ⁵ represents 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms). ), And p is a number from 1 to 3.

  Preferable specific examples of the organosilicon compound represented by the above general formula include t-butyl-methyl-dimethoxysilane, t-butyl-methyl-diethoxysilane, cyclohexyl-methyl-dimethoxysilane, and cyclohexyl-methyl-di. An ethoxysilane etc. are mentioned.

  In the sequential polymerization, propylene or propylene and another α-olefin having 2 to 8 carbon atoms are supplied in the first stage, and the temperature is 50 to 150 ° C. (preferably 50 to 100 ° C.) in the presence of the catalyst. The propylene homopolymer is obtained by polymerization under the condition of propylene partial pressure of 0.5 to 4.5 MPa (preferably 1.0 to 3.5 MPa). Subsequently, in the second stage, propylene and ethylene, or propylene and Ethylene and an α-olefin having 4 to 8 carbon atoms are supplied, and in the presence of the catalyst, the temperature is 50 to 150 ° C. (preferably 50 to 100 ° C.), and the partial pressures of propylene and ethylene are each 0.3 to 4.5 MPa ( Polymerization is preferably performed under the conditions of 0.5 to 3.5 MPa) to obtain a propylene-ethylene copolymer or a propylene-ethylene-α-olefin copolymer.

  The polymerization method may be any of batch, continuous and semi-batch. The first stage polymerization can be carried out in the gas phase or liquid phase. The second stage polymerization is carried out in the gas phase or liquid phase, preferably in the gas phase. The residence time in each stage is usually 0.5 to 10 hours, preferably 1 to 5 hours.

  In addition, when problems such as stickiness occur in the powder particles of the resulting propylene-based copolymer, after the polymerization in the first stage, the polymerization starts in the second stage in order to impart fluidity to the powder particles. It is preferable to add the active hydrogen-containing compound before or during the polymerization. Examples of active hydrogen-containing compounds include water, alcohols, phenols, aldehydes, carboxylic acids, acid amides, ammonia, amines, etc., and the amount used is usually titanium in the solid component of the catalyst. It is in the range of 100 to 1000 times mol for the atom and 2 to 5 times mol for the organoaluminum compound of the catalyst.

  As described above, the constituent material of the surface layer material includes the material (I) and the material (II), the former resin component is the above propylene copolymer, and the latter resin component is the above propylene copolymer. The proportion of the propylene copolymer is 50% by weight or more based on the total amount of the blend and other polypropylene resins.

  The polypropylene resin used for the material (II) is not particularly limited, and may be a copolymer containing a small amount (usually 5 mol% or less) of ethylene-derived units. Moreover, the ratio of the above-mentioned propylene-based copolymer to the total amount of the above-mentioned propylene-based copolymer and other polypropylene-based resin is preferably 70 to 99% by weight, and more preferably 80 to 99% by weight.

  Moreover, an elastomer can be mix | blended with said material (I) and material (II) in the range which does not inhibit the required performance. As the elastomer, in addition to the above-mentioned olefin elastomer and styrene elastomer, ethylene-propylene copolymer rubber (EPM), ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), ethylene-butene-1 copolymer rubber, ethylene -Styrene block copolymers such as ethylene-α-olefin copolymers such as propylene-butene-1 copolymer rubber, hydrogenated styrene-butadiene block copolymers, and hydrogenated styrene-isoprene copolymers. . The ratio of the elastomer is usually 20% by weight or less, preferably 10% by weight or less as a ratio with respect to the total amount of the resin and the elastomer.

  Moreover, a lubricant can be blended with the materials (I) and (II) for the purpose of improving scratch resistance. Examples of lubricants include organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydropolysiloxane, stearoamide, oxystearamide, oleylamide, erucylamide, laurylamide, palmitylamide, behenamide, etc. Higher fatty acid monoamide type, modified monoamide such as methylol amide, ethylol amide, etc., complex amide such as stearyl oleyl amide, N-stearyl erucamide, bisamide type higher grade such as methylene bisstearoamide, ethylene bisstearamide, etc. In addition to fatty acid amides such as fatty acid amides, polyethylene waxes generally added to olefinic resins can be mentioned. These can also be used in combination. The ratio of the lubricant is usually 20% by weight or less, preferably 10% by weight or less as a ratio to the resin.

  Furthermore, in addition to the above-described components, the propylene-based copolymer can be blended with other arbitrary blending components according to various purposes within a range not impairing the effects of the present invention. Examples of such components include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, and flame retardants. In addition to various additives such as antistatic agents, conductivity imparting agents, metal deactivators, molecular weight regulators, antibacterial agents, antifungal agents, and fluorescent brighteners, the above-described inorganic fillers and the like can be mentioned. In consideration of outdoor use, addition of an antioxidant, a light stabilizer, an ultraviolet absorber, and a colorant is particularly preferable. The proportion of the above compounding agent is usually 10% by weight or less, preferably 5% by weight or less as a proportion with respect to the resin.

  For the preparation of the material (I) or (II) containing various compounding components, for example, a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, a brabender, a plastograph, a kneader, etc. Is used.

  In the present invention, any of molding methods such as extrusion molding, injection molding, compression molding, and blow molding can be applied to molding a resin laminate composed of a resin substrate and a surface layer. Then, it may be molded to the other later or simultaneously. A coextrusion molding method is particularly suitable.

  The thickness of the surface layer is thinner than the resin substrate, and is usually 0.1 to 1 mm, preferably 0.2 to 0.5 mm. Further, although methods for measuring physical properties of the surface layer will be described later, from a practical viewpoint, D hardness is 65 or less (preferably 40 to 60), surface gloss is 5% or more (preferably 10 to 30), and scratch depth in a scratch test. 20 μm or less (preferably 18 μm or less) is required.

  Since the resin laminate of the present invention is excellent in surface appearance, flexibility, weather resistance, heat resistance, hot water resistance, and scratch resistance, it is a composite resin molded product used indoors and outdoors, especially roof molding, weather strips, windows. Automotive exterior parts such as moldings, flush mount moldings, side moldings, glass run channels, protective seats for seat seat rails, assist grips, automotive interior parts such as shift knobs, entrance door seals, architectural gaskets such as packing materials, handrails, table edges, desks Although it is suitable for edges and the like, it is particularly suitably used for automotive molding applications.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. The materials used in the following examples are as follows.

(1) Propylene copolymer:
Propylene-ethylene copolymer produced according to the method of Example 2 of JP-A-2001-226435 (ethylene content in copolymer: 11% by weight, proportion of part soluble in xylene at room temperature: 35% by weight) The ethylene content in the part soluble in xylene at room temperature: 18% by weight, the melting point peak temperature of the copolymer: 164 ° C.).

(2) Styrenic elastomer (A):
“Sumiflex QE533AE” (block PP (polypropylene): 23 wt%, styrene rubber: SEBS (poly [styren-b- (ethlene-co-butylene) -b-styrene): 29 wt%, paraffinic oil) : 40% by weight, linear low density polyethylene (LLDPE): 8% by weight, D hardness: 70)

(3) Styrenic elastomer (B):
"PP compound QP306B" manufactured by Apco (block PP: 70 wt%, SEBS: 13 wt%, paraffinic oil: 13 wt%, LLDPE: 4 wt%, D hardness: 55)

(4) Polypropylene resin composition:
"PP compound QN510P" manufactured by Apco (block PP: 70 wt%, talc: 30 wt%, flexural modulus: 3200 MPa, MFR (230 ° C, 21.18N): 0.6, specific gravity: 1.14)

(5) Polypropylene resin (A):
"PP compound QN620PD" manufactured by Apco (homo PP: 50 wt%, random PP: 50 wt%, flexural modulus: 1400 MPa, MFR (230 ° C, 21.18N): 6, specific gravity: 0.90)

(6) Polypropylene resin (B):
“NOVATEC PP MG2T” manufactured by Nippon Polypro Co., Ltd. (random PP: 100% by weight, flexural modulus: 1350 MPa, MFR (230 ° C., 21.18 N): 15)

(7) Silicone master batch:
“BY27-001” (PP: dimethylpolysiloxane = 50: 50 weight ratio) manufactured by Toray Dow Corning
(8) Carbon black masterbatch:
“F30940MM” manufactured by Dainippon Ink & Chemicals, Inc. (polyethylene: carbon black = 60: 40 weight ratio)

Example 1:
Blending 100 parts by weight of propylene copolymer and 1 part by weight of carbon black masterbatch, using a 30 mm same-direction twin screw extruder, melt kneading at a resin temperature of 230 ° C. and pelletizing to obtain a surface layer material Furthermore, using a single screw extruder, the resin temperature was set to 180 ° C., and a test piece for a surface layer material having a width of 25 mm and a thickness of 1 mm was molded.

  As a result of measuring the physical properties of the test piece for the surface layer material, the D hardness (based on JIS K6253) was 55, and the surface gloss (based on JIS Z8741) was 25%. Also, using a HEIDON scratch tester, scratching on a straight line with a conical sapphire needle with a vertical load of 100 g and a radius of 0.05 mm, the depth from the reference surface to the valley is measured with a surface roughness meter made by Tokyo Seimitsu Co., Ltd. It was 17 micrometers when measured.

  The material prepared above was used as the surface layer material, and the styrenic elastomer (A) (“Sumiflex QE533AE”) was used as the base material. Then, using two melt extruders, a surface layer resin temperature of 180 ° C. and a substrate resin temperature of 190 ° C. were set, and a laminate having a width of 25 mm, a surface layer thickness of 0.5 mm, and a substrate thickness of 2.0 mm was molded. Both materials were completely fused.

Example 2:
In Example 1, when preparing the surface layer material, 80 parts by weight of the propylene copolymer and 20 parts by weight of the polypropylene resin (B) (Novatech PP MG2T) were used instead of 100 parts by weight of the propylene copolymer. Except for the above, the physical properties of the test piece for the surface layer material were measured and laminate molding was performed in the same manner as in Example 1. The surface layer test piece had a D hardness of 60, a flaw depth of 11 μm, and a gloss of 35%. Further, the surface layer material and the base material were completely fused.

Example 3:
In Example 1, the physical properties of the test piece for surface layer material were measured and laminated molding was performed in the same manner as in Example 1 except that 5 parts by weight of the silicon master batch was further used when preparing the surface layer material. The surface layer test piece had a D hardness of 56, a flaw depth of 10 μm, and a gloss of 23%. Further, the surface layer material and the base material were completely fused.

Example 4:
In Example 1, except that a polypropylene resin composition (“PP compound QN510P”) was used as a base material, lamination molding was performed in the same manner as in Example 1. As a result, the surface layer material and the base material were completely fused. did.

Comparative Example 1:
In Example 1, a styrene-based elastomer (A) having a D hardness of 70 (“Sumiflex QE533AE”) was used in molding the surface layer test piece. As a result of measuring physical properties in the same manner as in Example 1 for the obtained test piece for surface layer material, the scratch depth was 45 μm, the D hardness was 70, and the gloss was 2.5%.

Comparative Example 2:
In Example 1, physical properties of the surface layer test piece were measured in the same manner as in Example 1 except that a styrene-based elastomer (B) “PP compound QP306B” having a D hardness of 55 was used when forming the surface layer test piece. And laminate molding. The surface layer test piece had a scratch depth of 22 μm and a gloss of 15%. Further, the surface layer material and the base material were completely fused.

Comparative Example 3:
In Example 1, when the test piece for the surface layer material was molded, polypropylene resin (A) (“PP compound QN620PD” was used, and styrene elastomer (“Sumiflex QE533AE” was used as the base material) was carried out. The physical properties of the test piece for the surface layer material were measured and laminated molding was performed in the same manner as in Example 1. The D hardness of the test piece for the surface layer material was 75, and the flexibility was lost, making bending difficult. The surface layer material and the base material were completely fused.

Claims (2)

A resin laminate obtained from a surface layer formed on the design surface side of the resin substrate and the resin substrate by and co-extrusion Ri formed, the resin substrate is disposed along the surface, olefin It consists of one or a plurality of materials selected from the group of resins, olefin elastomers, and styrene elastomers, and the surface layer is composed of material (I) or material (II). The resin component of material (I) is as follows: (1) - consists propylene copolymer which satisfies the condition (5), the resin component of the material (II), the total amount of and both consist the above propylene-based copolymer and other polypropylene resins propylene copolymer fraction of the polymer Ri der least 50 wt%, and the surface layer of the D hardness of above Ru 40-60 der resin laminate for automobile exterior parts, characterized in that for.
(1) A copolymer of propylene and another α-olefin having 2 to 8 carbon atoms.
(2) The proportion of the portion soluble in xylene at room temperature in the copolymer is 20 to 50 % by weight.
(3) The content of α-olefin other than propylene in the portion soluble in xylene at room temperature is 5 to 30% by weight.
(4) The melting point peak temperature is 160 ° C. or higher.
(5) Including at least two or more stages of polymerization, after obtaining a propylene homopolymer in the first stage, propylene and ethylene having essential components of propylene and ethylene in the second and subsequent stages Obtained by a production method for obtaining a copolymer with an α-olefin. The resin laminate according to claim 1 , wherein the surface layer has a thickness of 0.1 to 1 mm and is used for automotive molding.