JPH04214711A - Complex resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in impact resistance and coating properties and suitable as injection molded products, etc., by reacting a specific polyisocyanate with a polyol and a polyamine and then mixing the resultant polyurethane with a polyolefinic resin. CONSTITUTION:The objective composition is obtained by reacting (i) a polyol such as polyethylene glycol with (ii) a nonaromatic polyisocyanate such as ethylene diisocyanate and (iii) a low-molecular polyamine such as ethylenediamine, providing (A) a thermoplastic polyurethane resin having 800-3000000 number-average molecular weight, then mixing the prepared thermoplastic polyurethane resin with (B) a polyolefinic thermoplastic resin such as polypropylene having preferably 10,000-3,000,000 number-average molecular weight at preferably (5:95)-(95:5) ratio as the weight of solid content.

Description

Description: [0001] The present invention relates to an improved polyolefin composite resin composition useful for injection molded products, extrusion molded products, and the like. [0002] Polyolefin resins are widely used as materials for injection molded products, extrusion molded products, blow molded products, etc. due to their economic efficiency and ease of molding. However, polyolefin resins have problems due to the material itself, such as impact resistance in terms of strength and paintability in terms of surface properties. Various studies have been made to improve this, and compounding the resin by mixing other rubber components with the polyolefin resin is known as an effective method. [0003] However, although the impact resistance can be considerably improved by mixing a rubber component with the polyolefin resin, the paintability is still not sufficient. [Means for Solving the Problems] In view of the above-mentioned current situation, the present inventors have intensively studied polyolefin composite resin compositions having sufficient impact resistance, paintability, etc. The inventors have discovered that polyurethane resin has an epoch-making effect as a composite agent for polyolefin thermoplastic resins, and have arrived at the present invention. That is, the present invention comprises a polyolefin thermoplastic resin (1) and a thermoplastic polyurethane resin (2) derived from a polyol (a), a non-aromatic polyisocyanate (b) and a low molecular weight polyamine (c).
) is a composite resin composition consisting of The polyolefin thermoplastic resin (1) used in the present invention includes polyethylene, polypropylene, ethylene-α-olefin copolymer (ethylene-propylene copolymer, ethylene-butene-1 copolymer) ), olefin-diene copolymer (EPDM, etc.)
, ethylene-vinyl acetate copolymer, ethylene-(meth)
Examples include acrylic acid copolymers, chlorinated polypropylene, and maleic acid-modified polypropylene. The number average molecular weight of this polyolefin thermoplastic resin (1) is usually 1
0,000-3,000,000, preferably 10,0
00 to 1,000,000. [0006] The polyol (a
) include polyether diols and polyester diols. As polyether diol,
(2) alkylene oxide adducts of low-molecular-weight diols, (2) ring-opened (co)polymers of alkylene oxides and/or cyclic ethers, and the like. [0007] Examples of low-molecular diols in (2) include aliphatic low-molecular diols [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-,1,3-butanediol, neopentyl glycol, 1,6 -hexanediol, 1
, 8-octamethylene diol, alkyl dialkanolamine, etc.], low-molecular-weight diols having a cyclic group [e.g., those described in Japanese Patent Publication No. 1474/1983: bis(hydroxymethyl)cyclohexane, m- and P-xylylene glycol, Bis(hydroxymethyl)benzene, 1
,4-bis(2-hydroxyethoxy)benzene, 4,
4'-bis(2-hydroxyethoxy)-diphenylpropane (ethylene oxide adduct of bisphenol A)
etc.]; and mixtures of two or more of these. [0008]Alkylene oxides in (2) include alkylene oxides having 2 to 4 carbon atoms [ethylene oxide, propylene oxide, 1,2-,2,3-,1
, 3-butylene oxide, etc.]. [0009] The ring-opening (co)polymer (①) can be obtained by ring-opening polymerization or ring-opening copolymerization (block and/or random) of the alkylene oxide and/or cyclic ether (tetrahydrofuran, etc.) exemplified in the section (②). Here are the things you can get. Specific examples of polyether diols include:
polyethylene glycol, polypropylene glycol,
Polyethylene-polypropylene (block and/or random) glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and/or random) glycol, polytetramethylene-propylene (block and/or random)
glycol, polyhexamethylene ether glycol,
Examples include polyoctamethylene ether glycols and mixtures of two or more thereof. [0011] Polyester diols include (1) condensed polyester diols obtained by reacting low-molecular diols and/or polyether diols with a molecular weight of 1000 or less with dicarboxylic acids and/or hydroxymonocarboxylic acids, and (2) ring-opened polyester diols of lactones. Examples include polylactone diol obtained by polymerization. [0012] Examples of the low-molecular diol in (2) include those exemplified in (2). [0013] The polyether diol with a molecular weight of 1,000 or less among the above-mentioned polyether diols includes those with a molecular weight of 1,000 or less, such as polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, triethylene glycol; and two or more thereof. A mixture of the following and having a molecular weight of 1000 or less may be mentioned. In addition, dicarboxylic acids in (2) include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) ) and mixtures of two or more thereof. [0015] Examples of the lactone in (2) include γ-butyrolactone and ε-caprolactone. Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly(
Polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, polycarbonate diol; and mixtures of two or more thereof. The number average molecular weight of polyol (a) is usually
It is 500-5000, preferably 700-4000. Examples of the method for producing the condensed polyester diol (2) include the following methods (a) and (b). (a) Low molecular diol and/or polyether diol with a molecular weight of 1000 or less, dicarboxylic acid or its ester-forming derivative [for example, anhydride (maleic anhydride, phthalic anhydride, etc.), lower ester (dimethyl terephthalate, etc.), (2) can be obtained by reaction (condensation) with a halide, etc.]. (ii) By reacting (condensing) a polyether diol with a molecular weight of 1000 or less, a dicarboxylic anhydride, and an alkylene oxide (eg, ethylene oxide and/or propylene oxide), (ii) can be obtained. To illustrate the method for producing (2), (2) is obtained by adding a lactone to an initiator (low molecular diol and/or polyether diol and polyester diol with a molecular weight of 1000 or less). [0020] In polyol (a), a low molecular weight diol can be used in combination with these. Examples of the low-molecular-weight diol include the low-molecular-weight diol mentioned in the section ① and the glycol ester of monohydroxymonocarboxylic acid (for example, those described in JP-A-61-190717). The molecular weight of these low molecular diols is usually 62 to 5.
It is 00. The non-aromatic polyisocyanate (b) used in the present invention is an aliphatic polyisocyanate having 2 to 12 carbon atoms (excluding the carbon in the NCO group); ) 4-15 alicyclic polyisocyanate, carbon number (excluding carbon in NCO group) 8-1
Aroaliphatic polyisocyanates of No. 2 and modified products of these polyisocyanates (modified products containing carbodiimide groups, uretdione groups, uretoimine groups, urea groups, biuret groups, and/or isocyanate groups, etc.) can be used. Specific examples of such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate,
2,6-diisocyanate methyl caproate, bis(
Aliphatic polyisocyanates such as 2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene Alicyclic polyisocyanates such as diisocyanate and bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate; aromatic aliphatic polyisocyanates such as xylylene diisocyanate and diethylbenzene diisocyanate; and two or more of these Mixtures may be mentioned. Preferred among these are aliphatic diisocyanates and cycloaliphatic diisocyanates, and particularly preferred are isophorone diisocyanate and hexamethylene diisocyanate. In the present invention, as the low molecular weight polyamine (c), aliphatic polyamines, alicyclic polyamines, araliphatic polyamines, aromatic polyamines, etc. can be used. Specific examples of such polyamines include aliphatic polyamines such as ethylene diamine, propylene diamine, and hexamethylene diamine; isophorone diamine;
-Alicyclic polyamines such as diaminocyclohexane; Aroaliphatic polyamines such as xylylene diamine and diethylbenzenediamine; Aromatic polyamines such as tolylene diamine, diphenylmethane diamine, and methylenebis(2-chloroaniline); and two or more of these Mixtures may be mentioned. Preferred among these are aliphatic polyamines and alicyclic polyamines, and particularly preferred are isophorone diamine and 1,4-diaminocyclohexane. The molecular weight of these low molecular weight polyamines is usually 60 to 500. In the present invention, the number average molecular weight of the thermoplastic polyurethane resin (2) is usually 800 to 3,000,
000, preferably 1,000 to 1,000,000. The method for producing the thermoplastic polyurethane resin (2) is not particularly limited, and any known method may be used. For example, polyisocyanate (b) and polyol (a) are reacted in a molar ratio with an excess of isocyanate groups. A prepolymer with terminal isocyanate groups is made, and then a low molecular weight polyamine (c
). A one-step method in which three components, polyol (a), polyisocyanate (b), and low-molecular-weight polyamine (c) are reacted in one step, etc. can be performed. In the above method, polymerization is carried out in the presence or absence of a solvent. When the reaction is carried out in the presence of a solvent, the polyolefin thermoplastic resin (1)
Either method may be used, such as by removing the solvent after mixing with the resin, or by mixing the solution with (1) after converting the solution of (2) into a solid resin by removing the solvent. [0027] As a solvent, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.)
, ethers (dioxane, tetrahydrofuran, etc.)
, aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (chlorobenzene, trichlene, percrene, etc.), esters (ethyl acetate, butyl acetate, etc.), amides (dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), aliphatic hydrocarbons (n-hexane, n-heptane, isooctane, petroleum benzene, mineral spirit, etc.), alicyclic hydrocarbons (cyclohexane, etc.), and these two
Mixtures of more than one species are included. When producing the thermoplastic polyurethane resin (2), the ratio of reaction components (a), (b) and (c) is (NCO equivalent): (OH equivalent + active hydrogen equivalent of low molecular weight polyamine). 1:0.8-1.2, preferably 1:
The ratio may be adjusted to 0.9 to 1.1. [0029] The reaction temperature during the production of the thermoplastic polyurethane resin (2) may be the same as the temperature normally employed when converting urethane in the relevant industry, and when a solvent is used, it is usually 20°C to 100°C. When no solvent is used, the temperature is usually 20°C to 220°C, preferably 100°C to 200°C.
It is ℃. Amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) used in normal urethanization reactions to accelerate the reaction.
, tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, dibutyltin malate, etc.) may be used. Furthermore, if necessary, a polymerization terminator such as a monohydric alcohol (methanol, butanol, cyclohexanol, etc.), a monohydric amine (methylamine, dimethylamine, dibutylamine, cyclohexylamine, etc.), etc. can also be used. [0030] As a reaction apparatus for producing the thermoplastic polyurethane resin (2), those generally employed in the industry can be used. In the present invention, the ratio of polyolefin thermoplastic resin (1) to thermoplastic polyurethane resin (2) is usually 5:95 to 95:5 based on solid weight. The composition of the present invention contains a polyolefin thermoplastic resin (1) and a thermoplastic polyurethane resin (1).
2) A dispersant can be added if necessary to aid in dispersion. As this dispersant, Japanese Patent Application No. 2-131527 and Japanese Patent Application No. 2-131 filed by the present applicant can be used.
528 and the dispersants described in the specifications of Japanese Patent Application No. 2-181726. The amount of the dispersant used is 0.5 to 10% by weight based on the composite resin composition of the present invention. [0033] Further, other compounding agents may be added to the polyolefin composite resin composition of the present invention, if necessary. For example, pigments or dyes for coloring, inorganic fillers (talc, calcium carbonate, silica, glass fiber, etc.) for improving physical properties, organic modifiers (PP resin, AS resin, etc.)
, various stabilizers and softeners to improve light resistance and heat deterioration resistance,
Plasticizers etc. can be used. The amount of these other compounding agents used is 0 to 50% by weight based on the composite resin composition of the present invention. The composition of the present invention can be easily obtained by mixing the polyolefin thermoplastic resin (1), the thermoplastic polyurethane resin (2), and, if necessary, the above-mentioned dispersant and other compounding agents. Mixing temperature is usually 10~
The temperature is 350°C, preferably 100-300°C. [0035] The mixing time should be as short as possible to avoid thermal deterioration of each component, and is usually 0.5-6.
0 minutes, preferably 1 to 30 minutes. The mixing device is not particularly limited, and various known mixers can be used. Specific examples include an extruder, a kneader, a Banbury mixer, and a planetary mixer. [Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight. Production Example 1 121 parts of polytetramethylene ether glycol having a hydroxyl value of 112 was put into a four-necked flask equipped with a stirring bar and a thermometer, and the mixture was heated to 110% under reduced pressure of 3 mmHg.
The mixture was heated to ℃ and dehydrated for 1 hour. Next, 54 parts of isophorone diisocyanate was added to the flask, and 110 parts of isophorone diisocyanate was added to the flask.
A prepolymer was obtained by carrying out a reaction at ℃ for 10 hours. The free isocyanate content of the prepolymer was 5.8%. Next, 585 parts of toluene and 215 parts of ethanol were added and stirred, then 24 parts of 1,4-diaminocyclohexane was added and the reaction was carried out at 60°C for 2 hours, followed by 1.5 parts of dibutylamine. The polymerization reaction was stopped by stirring, and a thermoplastic polyurethane resin solution was obtained. This thermoplastic polyurethane resin solution was heated to 180°C,
After desolventizing by reducing the pressure to 20 mmHg, pulverization is carried out using liquid nitrogen as a refrigerant to obtain granular polyurethane resin (A).
I got it. Production Example 2 A granular polyurethane resin (B) was obtained in the same manner as Production Example 1 except that polytetramethylene ether glycol in Production Example 1 was replaced with polycaprolactone diol having a hydroxyl value of 112. Comparative Production Example 1 Polycaprolactone diol with a hydroxyl value of 112, 1
21 parts were added and heated to 110° C. under reduced pressure of 3 mmHg to perform dehydration for 1 hour. Subsequently, 54 parts of isophorone diisocyanate was additionally charged into the flask, and the reaction was carried out at 110° C. for 10 hours to obtain a prepolymer. The free isocyanate content of the prepolymer was 5.8%. followed by 1
, 4-butanediol, 10.9 parts were added to 19
After reacting at 0°C for 2 hours, the mixture was pulverized using liquid nitrogen as a refrigerant to obtain granular polyurethane resin (C). Example 1 Polypropylene (UBE-Polypro J manufactured by Ube Industries, Ltd.)
-609H, hereinafter abbreviated as PP), 80 parts of polyurethane resin (A), and maleic acid-modified polypropylene (
Amount of bound maleic acid 5%, Mw = 5000; dispersant) 3 parts were transferred using a twin-screw extruder (2D25- manufactured by Toyo Seiki Seisakusho Co., Ltd.).
S-type, 20mmφ, L/D=25) was melt-kneaded at a cylinder temperature of 190°C for 5 minutes, taken out into strands, broken with a pelletizer, and pelletized composite resin composition (R-I ) was obtained. Example 2
Polyurethane resin (A) (B
) A pellet-shaped composite resin composition (R-2) was obtained in the same manner as in Example 1 except that Comparative Example 1 Polyurethane resin (A) and (C)
A pellet-shaped composite resin composition (R') was obtained in the same manner as in Example 1 except that . Physical Property Measurement Example 1 Resin compositions (R-1), (R-2) and (R') and PP alone were injection molded to obtain test specimens for JIS testing. These Izod impact strength (JIS K71
10) and flexural modulus (JIS K7203) were measured. The results are shown in Table 1. In addition, as paintability, the paint residual rate (%) was determined by a grid test using the following method. The results are shown in Table 1. (Paintability test method) After the test piece was brought into contact with trichloroethane vapor for 45 seconds, a polyurethane paint (manufactured by Kansai Paint Co., Ltd.) was applied to the test piece to a film thickness of 20 μm, and the test piece was heated at 120° C. for 40 minutes. After drying, 10 grids of 1 mm in length and 1 mm in width are placed on this coating film.
The operation of rapidly peeling off the coating film at an angle of 45 degrees using cellophane adhesive tape was repeated twice in increments of 0, and the proportion (%) of the remaining coating film in a grid pattern was determined. [Table 1] [Effects of the Invention] The properties of the molded products obtained from the composite resin composition of the present invention are significantly improved compared to those obtained from each resin alone. It is. In a composite resin composition containing a large amount of polyolefin thermoplastic resin (1), the molded product has a higher content than that of (1) alone.
Impact resistance and paintability are improved at the same time. In particular, the improvement in paintability is epoch-making compared to conventional methods. Therefore, it is suitable for various molding materials that require impact resistance and paintability, such as automobile parts such as bumpers. In composite resin compositions containing a large amount of thermoplastic polyurethane resin (2), the molded product has much better releasability than (2) alone, and has significantly improved workability. Improved. Therefore, various molded products can be produced at lower cost than conventional products.

Claims (1)

[Claims] [Claim 1] Polyolefin thermoplastic resin (1)
and a thermoplastic polyurethane resin (2) derived from a polyol (a), a non-aromatic polyisocyanate (b) and a low molecular weight polyamine (c).