JP2001206951A - Composite resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a composite resin composition having excellent physical properties by effectively utilizing semi-rigid or rigid polyurethane resin waste and formulating reactive resins, non-reactive resins, polymer alloy of thermoplastic resins thereto. SOLUTION: The objective composite resin composition is formed by kneading crosslinked polyurethane resin together with reactive resins, non-reactive resins or alloy resins over a specific temperature to give the objective composite resin composition of cross-linked polyurethane resin with a reactive resin, non- reactive resin and alloy resin. The objective composite resin composition is obtained by formulating crosslinked polyurethane resin hydrolyzate and the solid fillers to the non-reactive resin and the alloy resins and kneading the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crosslinked polyurethane resin or a hydrolysis product thereof, and a thermoplastic resin containing a reactive resin, a nonreactive resin or a rubber elastic material.
Related to composite resin with seed.

[0002]

2. Description of the Related Art In recent years, with the deterioration of the global environment, the creation of an environment-friendly society has been demanded, and the study of the reuse of resin waste for the purpose of reducing environmental load and effectively using resources has been promoted. . Various studies have also been conducted on the recycling of resin parts in automobiles. In particular, resin bumpers are large external parts, and studies on material recycling are being actively conducted.

[0003] Incidentally, a polypropylene resin or a polyurethane resin is used for the resin bumper. The former is a thermoplastic resin that can be re-melted, and it is easy to re-mold and recycle waste materials, but the latter is a thermosetting resin that forms an insoluble / infusible molecular skeleton by a crosslinking reaction. If it is not treated, it cannot be recycled.

[0004] As a method of recycling the polyurethane resin bumper, a method of decomposing the resin by chemical treatment such as glycolysis, aminolysis or hydrolysis and returning it to the original material (chemical recycling), burning the resin to generate heat energy Method of recovery (thermal recycling), cutting, cutting and pulverizing resin as filling, filling material, leveling material, sound absorbing material, vibration damping material, etc., or as a substitute for rubber parts by adding a binder and pressing and compression molding The method used (material recycling) is exemplified.

[0005] In material recycling in which a waste material of a polyurethane resin bumper is mixed into a resin material or the like to obtain a recycled component, in order to prevent problems such as deterioration of material properties and surface quality due to poor dispersion of additives, the mixing property of both materials is reduced. It is important to increase. For that purpose, it is necessary to pulverize the waste material added to the resin. JP-A-50-154379 discloses a technique in which polyurethane foam scrap is pulverized, mixed as a thermoplastic resin, and injected or extruded.

Japanese Patent Application Laid-Open No. 57-45026 discloses thermoplastic molding by pulverizing waste thermosetting polyurethane resin to 1 mm or less and kneading it with a thermoplastic polyurethane resin. Further, Japanese Unexamined Patent Publication No.
Japanese Patent No. 45027 discloses a technique of pulverizing waste thermosetting polyurethane resin to 1 mm or less, adding a thermoplastic polyurethane resin and a vinyl chloride resin, and kneading the resulting mixture to carry out calendar processing.

When polyurethane resin powder is mixed into a thermoplastic resin or the like, it is important to finely pulverize the polyurethane resin in order to enhance the compatibility. There is no proposal, and lacks practicality. Further, in the above-mentioned conventional technology, the thermosetting polyurethane resin is simply mechanically pulverized and added as a filler for the thermoplastic resin. There is no description about the structural change and the effect on the material properties.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is different from a case where a crosslinked polyurethane resin powder is blended with another resin and merely mechanically blended.
It is an object of the present invention to provide a composite resin having new characteristics by being uniformly dispersed in a base resin with compatibility or affinity.

[0009]

The composite resin according to claim 1 is a partially hydrolyzed urethane obtained by kneading a crosslinked polyurethane resin and a reactive resin at a temperature not lower than the melting temperature of the reactive resin. It is a resin obtained by reacting at least a reactive crosslinked polyurethane resin in which at least half of the bonds have been broken and the reactive resin. The composite resin according to claim 5, wherein the crosslinked polyurethane resin and the reactive resin that have absorbed moisture are kneaded at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin and not lower than the melting temperature of the reactive resin. It is a resin obtained by cutting at least half of the hydrolyzed urethane bonds and reacting at least the modified crosslinked polyurethane resin and the reactive resin.

[0010] The composite resin according to claim 7 is obtained by kneading a crosslinked polyurethane resin and an olefin-based thermoplastic alloy resin that have absorbed moisture at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin. It is a resin obtained by mixing a deteriorated crosslinked polyurethane resin in which at least half of urethane bonds are decomposed and broken, and an olefin-based thermoplastic alloy resin.

[0011] The composite resin according to the ninth aspect of the present invention is characterized in that the matrix of the non-reactive resin or the olefin-based thermoplastic alloy resin containing the olefin-based rubber elastic material has a relatively high resin viscosity when melted. A resin in which a hydrolysis product of a crosslinked polyurethane resin having a relatively low viscosity when melted and having a solid filler as a core is dispersed in fine particles.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One of the present invention is a composite resin in which a crosslinked polyurethane resin is blended with at least one resin selected from a reactive resin, a non-reactive resin, and an alloy resin. The composite resin of the present invention can be formed as follows.

First Method A crosslinked polyurethane resin and a reactive resin are obtained by kneading under a temperature condition not lower than the melting temperature of the reactive resin. Second method The water-containing crosslinked polyurethane resin and the reactive resin are kneaded at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin and not lower than the melting temperature of the reactive resin. Third Method: A crosslinked polyurethane resin containing water and a non-reactive resin are kneaded under a temperature condition not lower than the hydrolysis temperature of the crosslinked polyurethane resin.

Fourth Method A crosslinked polyurethane resin containing water and a thermoplastic alloy resin containing a rubber elastic material are kneaded at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin. Fifth Method A crosslinked polyurethane resin containing water and a thermoplastic alloy resin containing a rubber elastic body are mixed at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin and not lower than the oxidation temperature of the thermoplastic alloy resin in air. Knead.

In the composite resin obtained by the first method, the crosslinked polyurethane resin is finely dispersed in the reactive resin by cutting the polyurethane crosslinking based on the reaction between the crosslinked polyurethane resin and the reactive resin, and the dispersed phase interface Crosslinks the polyurethane resin and the reactive resin. In the composite resin obtained by the second method, the cross-linking of the polyurethane resin is promoted by the reaction between the cross-linked polyurethane resin and the reactive resin and hydrolysis by the presence of moisture, whereby the first resin is cured.
The dispersion and bonding of the crosslinked polyurethane resin to the reactive resin can be further promoted more finely than in the case of the above method.

The composite resin obtained by the third method and the fourth method is a crosslinked urethane which is superior to the conventional composite by breaking the crosslink of the polyurethane resin by hydrolysis of the crosslinked polyurethane resin in the presence of moisture. Fine dispersion between the resin and the non-reactive or alloy resin can be realized. In addition, the composite resin obtained by the fifth method has an activity that is generated by the cross-linking of the polyurethane resin being cut by hydrolysis of the cross-linked polyurethane resin due to hydrolysis of the cross-linked polyurethane resin due to the presence of water and a carboxyl group generated by oxidizing a part of the olefin resin. The reaction with the group becomes possible, and higher compatibility can be expected as in the case of kneading with a reactive resin.

As a result, the same kind of composite resin can be finely dispersed, which has never existed before, and the physical properties of the composite resin can be improved. Another aspect of the present invention is a crosslinked polyurethane resin, or a hydrolysis product of a crosslinked polyurethane resin, a solid filler, a non-reactive resin, and one or more resins selected from thermoplastic alloy resins of a non-reactive resin. And a composite resin blended with

This composite resin can be formed as follows. Sixth Method The crosslinked polyurethane resin is mixed with the water-containing crosslinked polyurethane resin, the solid filler, and the non-reactive resin or the non-reactive resin alloy resin at a temperature not lower than the melting temperature of the non-reactive resin or the non-reactive resin alloy resin. Kneading is performed at a temperature higher than the hydrolysis temperature of the resin. Seventh Method The hydrolyzate of a crosslinked polyurethane resin and a solid filler and a thermoplastic alloy resin of a non-reactive resin or a non-reactive resin are mixed with each other at a temperature not lower than the melting temperature of the non-reactive resin or the alloy resin of the non-reactive resin. Knead under temperature conditions.

Eighth Method At least one of a crosslinked polyurethane resin containing water, a thermoplastic resin of a non-reactive resin or a non-reactive resin contains a solid filler, and an alloy resin of a non-reactive resin or a non-reactive resin. Above the melting temperature of
In addition, kneading is performed at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin. Ninth method In a state where at least one of a hydrolyzate of a crosslinked polyurethane resin and a thermoplastic alloy resin of a non-reactive resin or a non-reactive resin contains a solid filler, a non-reactive resin or a non-reactive resin Kneading is performed at a temperature higher than the melting temperature of the thermoplastic alloy resin.

In the seventh method and the ninth method, it is preferable that the melt viscosity of the non-reactive resin and the alloy resin of the non-reactive resin is relatively higher than the viscosity of the hydrolysis product of the crosslinked polyurethane resin. As a result, the hydrolysis product of the crosslinked polyurethane resin is aggregated so as to surround the solid filler due to the difference in viscosity during kneading and molding, whereby fine dispersion can be expected. As a result, it is possible to achieve fine dispersion which has not been achieved by a similar composite resin, and physical properties of the resin can be improved. In the sixth method and the eighth method, the cross-linking points in the cross-linked polyurethane resin are hydrolyzed and cut by moisture, and finely dispersed in the non-reactive resin or the non-reactive resin alloy alloy by shearing force during kneading. .

In the seventh and ninth methods, the hydrolysis product of the crosslinked polyurethane resin is finely dispersed in the non-reactive resin or the thermoplastic alloy resin of the non-reactive resin by the shearing force during kneading.

The crosslinked polyurethane resin of the present invention is a semi-hard or hard polyurethane resin containing a hydroxy compound, an isocyanate compound and a crosslinking agent as main components and obtained by reaction injection molding such as RIM molding or R-RIM molding.
This resin does not need to be limited to waste materials generated in the manufacturing process and waste materials collected from the market. New materials may be used, or new materials and waste materials may be mixed.

The hydroxy compound constituting the crosslinked polyurethane resin of the present invention is not particularly limited. For example,
Examples of the polyester compound include hydroxypolyesters prepared from polybasic acids such as phthalic acid, adipic acid and maleic acid and hydroxy compounds such as glycols, trimethylolpropane, hexanetriol, glycerin and pentaerythritol. Further, poly (oxypropylene ether) polyols, polyether polyols such as poly (oxyethylene-propylene ether) polyol, acrylic polyols, castor oil derivatives, tall oil derivatives, polypropylene glycol,
Examples include polyethylene glycol and other compounds having two or more hydroxyl groups.

This hydroxy compound may be used alone or in combination of two or more. Further, it may be linear or branched, and may have a bifunctional or higher hydroxyl group. The isocyanate compound constituting the crosslinked polyurethane resin of the present invention includes, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Examples include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, and derivatives such as toluene diisocyanate trimer and toluene diisocyanate urea polymer.

These isocyanate compounds may be used alone or in combination of two or more. Further, it may have a bifunctional or more isocyanate group. The isocyanate compound is not particularly limited, but preferably aromatic isocyanate is suitable for reaction injection molding. Examples of the cross-linking agent include amines such as hexamethylenediamine, 4,4'-diaminodiphenylmethane, and diethyltoluenediamine. These compounds may be used alone or in combination of two or more.

The hydrolysis product of the crosslinked polyurethane resin can be formed under the hydrolysis conditions described below, and the crosslinked polyurethane resin containing water is maintained at a temperature higher than its hydrolysis temperature and lower than the liquefaction temperature at which it thermally decomposes. can get. In this case, it can be obtained by treating the crosslinked polyurethane resin alone, and can also be obtained by treating in the presence of a thermoplastic resin.

The hydrolysis product of a relatively low-viscosity crosslinked polyurethane resin of the present invention is a hydrolysis product of a resin containing a hydroxy compound, an isocyanate compound and a crosslinking agent as main components and obtained by reaction injection molding. In this structure, the cross-linking is partially maintained and partially cut.
In addition, the viscosity at the time of kneading or molding is lower than the melt viscosity of the non-reactive resin or the alloy resin of the non-reactive resin.

In the present invention, if necessary, an alcohol-based auxiliary crosslinking agent such as triethanolamine, a synthetic wax,
Release agents such as metal soaps and silicone oils, stabilizers such as ultraviolet absorbers and antioxidants, triethylamine, N-
A catalyst such as methylmorpholine, triethylenediamine, dibutyltin dilaurate, a filler such as glass fiber or potassium titanate, a pigment, a colorant, and other additives may be added.

The reactive resin is not particularly limited as long as it has a functional group capable of reacting with an active group generated by crosslinking or hydrolysis of the crosslinked polyurethane resin and is melted by heating. Examples include thermoplastic resins such as polyamide resins and vinyl acetate copolymer resins, and thermoplastic resins having at least one functional group such as an ester group, a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and an oxazoline group. Specific examples include a maleic acid-modified polypropylene resin and an epoxy-modified polyethylene resin.

As the polyamide resin, 6-nylon,
12-nylon, 6,6 nylon and the like. Modified resins such as a copolymer of 6-nylon and 6,6 nylon, a copolymer of 6-nylon and 12-nylon, an alloy of 6-nylon and polypropylene resin, an alloy of 6-nylon and ABS resin, and the like. . The ratio between the crosslinked polyurethane resin and the reactive resin is not particularly limited.

Further, a monomer or an oligomer having a functional group capable of reacting with an active group generated by crosslinking or hydrolysis of the crosslinked polyurethane resin may be added. For example, amine compounds such as triethanolamine and diethyltoluenediamine, acid anhydrides such as maleic anhydride, monomer compounds such as organic metal compounds, thermosetting resins such as amino resins and phenol resins, and oligomers such as liquid rubber. Compounds.

The non-reactive resin is a resin having no functional group capable of reacting with an active group generated by crosslinking or hydrolysis of a cross-linked polyurethane resin. No, but melting temperature is 300
It is desirable to use a resin having a temperature of not more than ℃. This is because the polyurethane resin is decomposed and liquefied when left at a temperature of 310 ° C. or more for a long time.

The non-reactive resin or alloy resin having a relatively high viscosity is a resin having no active group capable of reacting with an active group generated by cross-linking or hydrolysis of a cross-linked polyurethane resin. Resin. Furthermore, there is no particular limitation as long as the viscosity in the molten state of the resin such as kneading or molding is higher than the viscosity of the polyurethane resin hydrolysis product, but a resin having a melting temperature of 300 ° C. or lower is desirable. This is because the polyurethane resin is decomposed and liquefied when left at a temperature of 310 ° C. or more for a long time.

The ratio of the non-reactive resin or the non-reactive resin in the alloy resin in the composite resin is such that the non-reactive resin or the non-reactive resin alloy resin can maintain its structure as a matrix component. If there is no limit,
The range is preferably from 30% by weight to 99% by weight in consideration of moldability and the like. In particular, 50% by weight for applications requiring mechanical properties
It is desirable to set the above mixing ratio.

Examples of the non-reactive resin include an olefin resin such as a polypropylene resin and a polyethylene resin, and a thermoplastic polyurethane resin. Further, the ratio between the crosslinked polyurethane resin and the non-reactive resin is not particularly limited. The kneading at a temperature higher than the melting temperature is a treatment at a temperature higher than a temperature at which a usual thermoplastic resin can be kneaded.

When the semi-rigid or hard cross-linked polyurethane resin and the reactive resin are kneaded at a temperature higher than the melting temperature of the reactive resin, the cross-linked polyurethane resin does not need to absorb moisture. The alloy resin of the present invention is a polymer multi-component resin composed of a rubber elastic body and a thermoplastic resin, and includes a copolymer type and a polymer blend type. Examples of the copolymer system include block and graft copolymers.
Examples of polymer blends include physical blends such as melt blends and blends with compatibilizers, and chemical blends such as polymer complexes, solution grafts, interpenetrating polymer networks, and reactive processing. These resins may be used alone or in combination of two or more.

As the rubber elastic body, acrylic rubber, chlorinated polyethylene, ethylene-propylene rubber,
Examples include ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, and ethylene-acrylic acid copolymer. Examples of the thermoplastic resin component include a polystyrene resin, a polypropylene resin, a polyethylene resin, and a polymethyl methacrylate resin.

Particularly, in the present invention, an alloy resin containing an olefin rubber elastic body and an olefin thermoplastic resin as main components is preferable. Examples of the olefin-based thermoplastic resin include a polypropylene resin and a polyethylene resin. If the olefin-based thermoplastic resin is a main component, it may contain a resin component other than the olefin-based resin. Further, a rubber component or the like may be added to the olefin-based thermoplastic resin as a copolymer.

The olefin-based rubber elastic body includes ethylene,
It is a rubber containing a copolymer composed of two or more olefin compounds such as propylene and butylene as a main component. If the olefin rubber is a main component, a diene rubber or the like may be contained as a copolymer component. Specific examples include ethylene-propylene rubber, ethylene-propylene-diene rubber, and ethylene-butylene rubber.

The ratio between the olefin-based thermoplastic resin and the olefin-based rubber elastic body is not particularly limited, but it is desirable that the olefin-based thermoplastic resin be a large alloy resin. The olefin rubber elastic body and the olefin thermoplastic resin may be used alone or in combination of two or more. The alloy resin is not particularly limited as long as it is a resin that can be melted by heating, but a resin having a melting temperature of 300 ° C. or less is desirable. This is because the polyurethane resin is decomposed and liquefied when left at a temperature of 310 ° C. or more for a long time.

The ratio between the crosslinked polyurethane resin and the alloy resin is not particularly limited. The solid filler of the present invention is not fibrous, and is not particularly limited as long as it is a filler generally added to a resin material or the like, but it is necessary that the solid filler does not melt or decompose during kneading. Examples of the solid filler include inorganic materials such as talc, alumina, silica, calcium carbonate, and mica, silicone resins, Teflon (registered trademark) resins,
An organic filler such as a phenol resin is used. In particular, it is preferable to use talc as the solid filler.

These may be used alone or in combination of two or more, and may be subjected to a surface treatment or the like within a range not to impair the present invention. The method of adding the solid filler is not limited, and may be added at the time of kneading, or may be contained in the resin material used. The particle size of the solid filler is 100 μm in consideration of the effect on mechanical properties and surface quality.
It is desirable to do the following. Further, in order to enhance the core material effect of fine dispersion, the particle size of the solid filler is preferably 10 μm or less.

The ratio of the solid filler is not particularly limited, but is desirably determined in consideration of the ratio with the hydrolysis product of the crosslinked polyurethane resin. In particular, the weight ratio of crosslinked polyurethane resin hydrolysis product to solid filler is from 5: 1 to 1: 2.
In the case of the composite resin in the range of 0, the core material effect of the solid filler is exhibited, and good mechanical properties can be expected. The relatively low-viscosity cross-linked polyurethane resin hydrolysis product is a hydrolyzate of a resin obtained by reaction injection molding, containing a hydroxy compound, an isocyanate compound and a cross-linking agent as main components, and partially having cross-linking bonds. It is a structure that is maintained and partly cut. Further, it is a resin whose viscosity at the time of kneading or molding is lower than the melting temperature of the non-reactive resin or the alloy resin of the non-reactive resin.

The crosslinked polyurethane resin hydrolysis product can be obtained by maintaining the crosslinked polyurethane resin containing water at a temperature higher than its hydrolysis temperature and lower than the liquefaction temperature. The hydrolysis product of the crosslinked polyurethane resin can be obtained by treating the crosslinked polyurethane resin alone, and can also be obtained by treating in the presence of a thermoplastic resin.

In the present invention, various additives such as other fillers, coloring agents such as carbon black, pigments, antioxidants, ultraviolet absorbers, flame retardants and mold release agents may be used as needed. . In the present invention, it is necessary to use a moisture-containing crosslinked polyurethane resin and knead it with the alloy resin at a temperature not lower than its hydrolysis temperature.

Further, when kneading at a temperature higher than the oxidation temperature of the alloy resin, an active group such as a carboxyl group is generated in the alloy resin, and an alloying reaction with the polyurethane resin can be expected. For example, in the case of a combination of a urethane bumper and an olefin alloy resin, the temperature is preferably 200 ° C. or more and 300 ° C. or less, and more preferably a temperature range of 230 ° C. to 280 ° C. or less. This is because, when the temperature is low, it takes a long time for the treatment, and the bonding between the polyurethane resin and the alloy resin cannot be expected. On the other hand, if it is too high, the polyurethane resin is liquefied or the alloy resin undergoes thermal deterioration to deteriorate the material properties.

Hydrolysis Conditions It is important that the semi-rigid or hard cross-linked polyurethane resin is heated to a temperature higher than the temperature at which it is hydrolyzed, and that the cross-linked polyurethane resin absorbs moderate moisture. It is preferable that the moisture absorption is at least 0.1% or more after being not subjected to the drying treatment before the treatment. The upper limit of the moisture absorption is 10%. If the amount of moisture absorption exceeds 10%, the treatment becomes difficult due to steam generated during kneading, which is not preferable. The water content is more preferably in the range of 0.5 to 6%.

Even if the crosslinked polyurethane resin does not contain water, it may be in the coexistence of water, and water may be added to the extent that a moisture absorption of 10% or less is obtained during the hydrolysis treatment.
As a guide for controlling the amount of water, it is sufficient that the amount is more than about 0.1%. Further, a compound containing an active hydrogen or an organometallic compound may be added for the purpose of promoting the decomposition reaction,
Further, other additives may be added as long as the present invention is not impaired.

In the present invention, since the cross-linking point of the semi-rigid or hard cross-linked polyurethane resin is cut with heat and moisture, the desired treated product cannot be obtained unless the water is volatilized during the treatment. The treatment temperature is desirably not less than the hydrolysis temperature of the crosslinked polyurethane resin and not more than the liquefaction temperature.

For example, in a polyurethane resin bumper,
A range from 200 ° C. to 310 ° C. is desirable. This is because if the processing temperature is lower than 200 ° C., the processing time becomes longer, which is not practical. Conversely, if the treatment temperature is too high, not only is the liquefaction or gasification not possible to obtain the target product, but also harmful components such as cyan may be generated, which is not preferable. There is no particular limitation on the heating means, but it is desirable that heating can be performed uniformly in a short time.

The processing time varies depending on the composition of the crosslinked polyurethane resin, the processing temperature, the structure of the processing apparatus, and the like, and is determined as appropriate. Kneading The device for kneading the crosslinked polyurethane resin, the reactive resin, and the non-reactive resin may be any kneading device provided with a heating means, and examples thereof include a flat roll, an extruder, and a kneader. The reactive resin and the non-reactive resin may be used alone or in combination of two or more.

In particular, a screw-type extruder is desirable as a processing apparatus because it can suppress volatilization of water and can perform continuous processing. In the case of processing a large component such as a bumper, the average particle diameter is larger than 1 mm and 50 mm in advance.
It is desirable to coarsely pulverize below. In addition, various additives such as a stabilizer, a coloring agent, a filler, and a flame retardant may be added at the time of kneading as long as the object of the present invention is not impaired.

Composite Resin In the composite resin obtained by the present invention, a crosslinked polyurethane resin, a reactive resin and a non-reactive resin are finely dispersed and dispersed. Therefore, the following effects are obtained as compared with the case where a mechanically pulverized material is simply added. First effect Even if coarse particles larger than 1 mm are used, they can be dispersed as fine particles in the resin. Second effect Surface quality and fracture resistance are improved by finely dispersing the crosslinked polyurethane resin. Third effect Compatibility with the non-reactive resin is improved by the action of the active group generated by the cross-linking cleavage of the cross-linked polyurethane resin and the polar group present in the non-reactive resin. Fourth Effect The above characteristics cannot be expected with a composite resin to which conventional crosslinked polyurethane resin particles obtained by mechanical pulverization are added. Fifth Effect Compatibility with the resin is improved by the effect of the polar group (reactive group). Sixth effect When the composite resin is deformed, the interface between the fine particles of the hydrolysis product of the crosslinked polyurethane resin and the non-reactive resin or the alloy resin of the non-reactive resin is peeled off, resulting in a fine void (pupil phenomenon). To absorb the deformation energy. Seventh Effect The interface serves as a starting point of microcraze, so that deformation energy can be absorbed. This improves the mechanical properties.

The above characteristics cannot be expected in a composite containing conventional crosslinked polyurethane resin particles obtained by mechanical pulverization. The particle size of the polyurethane resin shearing treatment and the particle size of the fine particles of the crosslinked polyurethane resin hydrolysis using the solid filler as a nucleus are appropriately determined because the required size differs depending on the purpose of use.

For example, in the case of a composite resin of a crosslinked polyurethane resin and a polypropylene resin, the particle size of the polyurethane resin is desirably 200 μm or less. This is not preferable because an increase in the particle diameter causes a poor appearance of the molded product or a decrease in mechanical strength due to poor dispersion. The degree of the reaction between the crosslinked polyurethane resin and the reactive resin is appropriately determined depending on the purpose of use and required characteristics.

The degree of cross-linking of the cross-linked polyurethane resin for obtaining the composite resin is preferably at least half, preferably most of the urethane bonds cut. this is,
This is because if the urethane bond is not sufficiently cut, fineness does not occur even when a shearing force is applied. It is desirable that at least half of the urea bonds are not cleaved. This is because if a large number of urea bonds are cut, the liquefaction will result in liquefaction, so that the desired treated product can be obtained.

In addition, the composite resin of the present invention can be expected to improve the compatibility by the effect of the active group even if the polar group is not present in the blend partner material even if the polar group is not present. The presence of the polar group improves the affinity and wettability, and thus facilitates mixing with the resin. Furthermore, it becomes difficult to be charged by the effect of the hydroxyl group. The kneading apparatus is not particularly limited, but desirably, a screw-rotating kneader is used as a processing apparatus because effects such as prevention of water diffusion, continuous processing, and high kneading with shearing force can be obtained.

[0058]

EXAMPLE As an example of the treatment of a crosslinked polyurethane resin, R-
A case where a polyurethane resin bumper manufactured by RIM molding is used will be described. As a raw material, polypropylene glycol, diethyltoluenediamine, and 4,4′-diphenylmethane diisocyanate, which are raw materials of a polyurethane resin bumper material, were used, and a single fiber whisker of potassium titanate was used as a reinforcing material. These raw materials were molded as a polyurethane resin having a thickness of about 3 mm by an RIM molding machine, and then roughly pulverized by a hammer mill to about 5 mm (referred to as a coarsely pulverized polyurethane resin material).

For comparison with a coarsely pulverized polyurethane resin material, a RIM molded article having the same composition was mechanically pulverized,
A finely pulverized polyurethane resin material having an average particle size of 100 μm was produced. As the non-reactive resin, a homo-type polypropylene resin (H501) manufactured by Sumitomo Chemical Co., Ltd. was used. As the alloy resin, a homo-type polypropylene resin (H501) manufactured by Sumitomo Chemical Co., Ltd., and ethylene propylene rubber as a rubber component (Esprene V0115 manufactured by Sumitomo Chemical Co., Ltd.):
Propylene content 22%) and ethylene butene rubber (Esprene N0372 manufactured by Sumitomo Chemical Co., Ltd .: butene content 13)
%).

As the solid filler, talc having an average particle size of about 5 μm (untreated product) was used. The following was used as a processing apparatus. Apparatus 1: Twin screw extruder AS-30-2 type (L / D = 30) manufactured by Nakatani Machine Equipment 2: Twin screw kneader NEX-T60 manufactured by Kobe Steel + Single screw kneader Equipment 3: Japan Steel Works Twin extruder TEX-3α
(L / D = 45.5) The following was used as a hydrolysis product of the crosslinked polyurethane resin. The coarsely pulverized polyurethane resin material in a natural moisture absorption state (moisture absorption: about 0.8%) was extruded using the apparatus 1 and used (referred to as a crosslinked polyurethane resin hydrolysis product). The processing temperature was 260 ° C., and the processing was performed with the extruder head open. The residence time of the material at this time is about 60 seconds.

Example 1 Composite of Crosslinked Polyurethane Resin and Reactive Resin

[0062]

[Table 1] 30% of the above coarsely pulverized polyurethane resin material (hereinafter referred to as PU coarsely pulverized material) was added to a polyamide (PA) -based resin, and the influence on physical properties and the dispersion state were evaluated. Table 1 shows the composition of the resin and PU.

The PA resin includes 12PA manufactured by Ube Industries, Ltd.
Resin (3024U), 6PA / 12PA-copolymer resin (7125U) and soft 12 made by Dainippon Ink and Chemicals, Inc.
Alloy resin of PA resin (Greak N-1200) and 6PA resin manufactured by Chisso Chemical Co., Ltd. with polypropylene resin (Embnite H200K, containing 25% glass fiber)
Was used.

For kneading the PA resin and the PU coarsely pulverized product,
Using the twin-screw extruder of the above-described apparatus 1, the mixture was pelletized and taken out. Next, test pieces were prepared by injection molding and used as evaluation materials. Table 2 shows the extrusion conditions and molding conditions for each resin. PA-based resin and PU coarsely pulverized material were used after removing water by vacuum drying.

[0065]

[Table 2] For comparison, the same treatment was performed using a polypropylene (PP) resin (Noblen AZ564) manufactured by Sumitomo Chemical Co., Ltd. as a non-reactive resin. However, the above-mentioned finely pulverized polyurethane resin material was used as PU.

Table 3 shows the results of the tensile test of the test pieces and the results of visual observation of the dispersion state of PU. In Table 3,
Example No. Nos. 1 to 3 and Comparative Example Nos. There is a clear difference from the tensile elongation of 1a, indicating that the present invention improves the mechanical properties.

Also, in Example No. In the visual observation results of Nos. 1 to 4, PU particles were not recognized, but Comparative Example Nos.
In 1a, the presence of PU particles was confirmed. From the above, the composite resin obtained by kneading the reactive resin of the present invention and the crosslinked polyurethane resin at the melting temperature of the reactive resin, the crosslinked polyurethane resin reacts with the reactive resin nylon to increase the compatibility. ing. On the other hand, when kneaded with the polypropylene resin of the non-reactive resin of the comparative example, no reaction occurs between the crosslinked polyurethane resin and the polypropylene resin, and the tensile strength is insufficient.

[0068]

[Table 3]

Example No. 1 and Comparative Example No. 1. PU of 1a
The results of observing the dispersion state of the powder particles with a scanning electron microscope are shown in FIG. 1 and FIG. 2, respectively. Example No. in FIG. In No. 1, the presence of PU powder particles was not recognized,
Whiskers contained in the PU powder are dispersed in the PA resin. That is, it is understood that the plasticization of the PU powder and the reaction with the PA resin progressed in the kneading process, and the PU powder was uniformly dispersed in the PA resin.

On the other hand, in Comparative Example No. 1
In a, even if the twin-screw extrusion process and the injection molding are performed, P
There was no change in the shape of the U powder, and PU powder particles of 100 μm or more were observed in the test piece. From the above results, the crosslinked polyurethane resin and the reactive resin can be easily reacted by kneading at a temperature higher than the melting temperature of the reactive resin to form a composite resin having improved physical properties. On the other hand, in a composite resin obtained by kneading a non-reactive resin and a dry cross-linked polyurethane resin, the cross-linked polyurethane resin exists as it is, and the mechanical properties cannot be enhanced. Therefore, it can be seen that the dispersion state of PU is different between the example and the comparative example.

(Example 2) 6PA resin manufactured by Ube Industries (10
To 22B), 30% of the coarsely crushed polyurethane resin material having a moisture absorption of about 0.8% was added, and the mixture was kneaded at 240 ° C. by the twin-screw extruder of the apparatus 1. The strand obtained by this twin-screw extrusion process has rubber elasticity,
Remelting by heat was not possible. From this, it was found that the PU powder reacted with the PA resin, and a new modified resin was obtained.

The obtained modified resin can be used as a rubber elastic material for applications such as molding materials. From the above results, the composite resin obtained by kneading the crosslinked polyurethane resin and the reactive resin that have absorbed moisture at a temperature equal to or higher than the hydrolysis temperature of the crosslinked polyurethane resin and equal to or higher than the melting temperature of the reactive resin is obtained by the conventional mechanical pulverization. It can be seen that the characteristics are different from those of the composite resin obtained by kneading the powder obtained in the above. Example 3 30% of the above coarsely ground polyurethane resin material having a moisture absorption of about 0.8% was added to a non-reactive resin PP resin (Nobrene AZ564) manufactured by Sumitomo Chemical Co., Ltd. A kneading process was performed. In this study, a 250 ° C. treatment was performed using a twin-screw kneader, and then a single-screw kneader (2
(10 ° C.). After drying the pellets, test pieces were prepared by injection molding (190 ° C.).

For comparison, the same treatment was carried out using the finely ground polyurethane resin material in a dry state. Table 4 summarizes the evaluation contents of the third embodiment.

[0074]

[Table 4] Table 5 shows the tensile test results of the test pieces and the results of visual observation of the dispersion state of the PU powder.

In Table 5, Example No. 6 and the tensile elongation of Comparative Example No. 6. There is a clear difference from the tensile elongation of 2a, which indicates that the present invention improves the mechanical properties. Also, in Example No. No PU particles were observed in the visual observation results of Comparative Example No. 6, PU in 2a
The presence of particles could be confirmed. From the above, it can be seen that the composite resin obtained by the present invention has different characteristics from the composite resin obtained by kneading PU powder obtained by mechanical pulverization.

[0076]

[Table 5] Example No. 6 and Comparative Example No. 6. FIGS. 3 and 4 show scanning electron micrographs of the dispersion state of the PU powder particles 2a.
Shown in

Photograph Example No. 3 in FIG. In No. 6, PU powder and polypropylene (PP) are mixed so as to be hard to distinguish. In other words, it can be seen that the PU was plasticized by hydrolysis during the kneading process, and the PU was uniformly dispersed in the PP due to the shearing force during kneading. On the other hand, Comparative Example N shown in FIG.
o. In 2a, the shape of the powder did not change even after the twin-screw extrusion treatment and injection molding, and a PU powder of 100 μm or more was observed in the test piece.

From the above results, the composite resin obtained by kneading the crosslinked polyurethane resin and the non-reacted resin that have absorbed moisture at a hydrolysis temperature or higher can be used as a composite resin composition obtained by a conventional mechanically pulverized product. In comparison, it is clear that the mechanical properties are excellent and the dispersion state of PU is different. (Example 4) Low density polyethylene (PE) manufactured by Mitsubishi Chemical Corporation
30% of the coarsely ground polyurethane resin material having a moisture absorption of about 0.8% was added to the resin (LJ800), and kneading treatment was performed using the apparatus 2.

In this study, treatment was performed at 250 ° C. (above the hydrolysis temperature) with a twin-screw kneader, and then a single-screw kneader (21
(0 ° C.) and pelletized by drawing the strand. After drying the pellets, test pieces were prepared by injection molding (190 ° C.). For comparison, the same treatment was performed at a temperature of 150 ° C. (at a hydrolysis temperature or lower) using the finely ground polyurethane resin material in a dry state.

Table 6 summarizes the evaluation results of Example 4.

[0081]

[Table 6] Table 7 shows the results of the tensile test of the test pieces and the results of visual observation of the PU dispersion state.

In Table 7, the No. 7 and the tensile elongation of Comparative Example No. 7. There is a clear difference from the tensile elongation of 3a, which indicates that the composite resin of the present invention improves the mechanical properties of the molded product. In addition, in Example No. No PU particles were observed in the result of the visual observation of Comparative Example No. 7; In 2a, the presence of PU particles was confirmed.

[0083]

[Table 7] From the above, it can be seen that the composite resin obtained according to the present invention has different characteristics from the conventional composite obtained by mixing mechanically pulverized products. Further, it can be seen that, in the composite resin composition of the present invention, by treating the wet PU at a temperature equal to or higher than the hydrolysis temperature, it is possible to improve the mechanical properties, which are greatly reduced in the prior art.

(Example 5) As an alloy resin, a polypropylene resin bumper material which is an alloy resin of a polypropylene resin and a polyolefin rubber was used. This was roughly pulverized with a hammer mill to about 16 mm square or less to obtain a coarsely pulverized alloy resin material. For comparison, a polypropylene resin (Nobrene AZ564) manufactured by Sumitomo Chemical Co., Ltd. (referred to as PP material) was used. Table 8 shows the composition.

The following apparatus was used as the processing apparatus. Apparatus 4: Twin screw extruder with φ48 L / D = 41.6 Apparatus 5: Injection molding machine Injection molding machine manufactured by Meiki Co., Ltd. with a clamping pressure of 350 tons The coarsely pulverized alloy resin material (referred to as processing material 2 in Table 8) Then, 30 wt% of the above coarsely ground polyurethane resin (referred to as treatment material 1 in Table 8) was added thereto, and the influence on physical properties and the dispersion state were evaluated. For comparison, the single treatment of the coarsely pulverized alloy resin material (referred to as Comparative Material 1 in Table 8) and the combination of the PP material and the finely pulverized polyurethane resin material were also evaluated.

[0086]

[Table 8] For kneading, the twin-screw extruder of the above-described apparatus 4 was used to pelletize and take out. Next, a test piece was prepared by injection molding of the device 5 and used as an evaluation material. Table 9 shows the extrusion conditions and molding conditions for each resin. The resin temperature of the twin screw extrusion is higher than the oxidation temperature of the alloy resin.

[0087]

[Table 9]

[0088]

[Table 10] In the twin-screw extrusion treatment, the alloy resin and the coarsely pulverized PU were used without being dried. At this time, the moisture absorption of the polyurethane resin was about 0.8%.

Table 10 shows the results of the tensile test of the test pieces and the results of visual observation of the dispersion state of PU. In Table 10, Example No. Nos. 8 and 9 and Comparative Example Nos. 4
a, there is a clear difference from the tensile elongation of 5a, indicating that the present invention improves the mechanical properties. From the above, the composite obtained by kneading at a temperature equal to or higher than the hydrolysis temperature of the crosslinked polyurethane resin (250 ° C.) with the alloy resin comprising the hydrated crosslinked polyurethane resin and the rubber elastic body and the thermoplastic resin is obtained by mixing the non-alloy resin Comparative Example No. 4a, 5
It can be seen that the mechanical properties are improved as compared with the composite of a.

Example 6 Non-reactive resin homo PP (H
No. 501) and talc as a solid filler and a crosslinked polyurethane resin (hereinafter abbreviated as treatment material 3) in a natural moisture absorbing state (moisture absorption: about 0.8%). Nos. 10 to 13 and Comparative Example Nos. 6a to 12a were prepared. Table 11 shows each composition ratio.
(The values described below are expressed in parts by weight).

Each of the examples and the comparative examples was produced by using the twin screw extruder of the above-mentioned apparatus 3, pulled into a strand, and pelletized and taken out. Next, the pellets were dried and injection-molded to produce test pieces, which were evaluated. In the extrusion process, the homo PP, talc, and the treatment material 3 were weighed and mixed and kneaded simultaneously. The extrusion conditions were a resin temperature of 260 ° C., a screw rotation speed of 500 rpm, and a residence time of about 2 minutes. The injection molding conditions were a resin temperature of 190 ° C. and a mold temperature of 60 ° C.

In the evaluation test, a notched Izod impact test (according to JIS K7110) was carried out at normal temperature.
Table 12 summarizes the evaluation contents. Comparative Example N of Table 12
o. In 6a to 8a, when talc as a solid filler is added to Homo PP, the Izod impact value decreases as the amount of talc increases. Comparative Example No. In 9a to 12a, the Izod impact value of the homo PP is improved due to the effect of adding the polyurethane resin. On the other hand, Example No. In Comparative Examples Nos. 10 to 13, the PU resin and talc were added.
The Izod impact value is higher than 9a to 12a,
It can be seen that the composite resin of the present invention is effective for improving mechanical properties.

[0093]

[Table 11]

[0094]

[Table 12] (Example 7) Homo PP (H50) which is a non-reactive resin
1) Example using ethylene propylene rubber (V0115), ethylene butene rubber (N0372), talc as a solid filler, and PU powder (moisture absorption: about 0.8%) in a natural moisture absorbing state (treated material 3). No. 14 to 15 and Comparative Example Nos. 13a to 15a were prepared. Each composition ratio is shown in Table 13.

[0095]

[Table 13] Each of the examples and the comparative examples was produced using the twin-screw extruder of the above-described apparatus 3, pulled into a strand, and then pelletized and taken out. Next, the pellets were subjected to a drying treatment, and test pieces were prepared by injection molding, which were used as evaluation materials.

In the extrusion process, homo PP, ethylene propylene rubber (EPR), ethylene butene rubber (EB) were used.
R), talc, and treatment material 3 were weighed and mixed and kneaded simultaneously. The extrusion conditions were a resin temperature of 260 ° C., a screw rotation speed of 500 rpm, and a residence time of about 2 minutes. The injection molding conditions were a resin temperature of 190 ° C. and a mold temperature of 60 ° C. A notched Izod impact test (according to JIS K7110) was performed at room temperature, and the evaluation contents are shown in Table 14.

From the results in Table 14, it can be seen that the Izod impact value is improved by the combination of the talc as the solid filler and the treated material 1 of the PU resin, and the composite resin of the present invention is effective for improving the mechanical properties. .

[0098]

[Table 14] (Example 8) Homo PP (H501), ethylene propylene (V0115), ethylene butene rubber (N0372)
Using the talc as a solid filler and a crosslinked polyurethane resin (treated material 3) in a natural moisture absorbing state (moisture absorption: about 0.8%), the product of Example No. 1 was used. 16 to 20 and Comparative Example Nos. 16a
Was prepared. Table 15 shows the composition ratios.

[0099]

[Table 15] Each of the examples and the comparative examples was produced using the twin-screw extruder of the above-described apparatus 3, pulled into a strand, and then pelletized and taken out.

In this example, homo-PP, ethylene propylene, ethylene butene rubber, and talc were weighed and mixed and kneaded simultaneously with an extruder to prepare a master batch.
Extrusion conditions were as follows: resin temperature 200 ° C, screw rotation speed 50
0 rpm and a residence time of about 2 minutes. Next, a predetermined crosslinked polyurethane resin was added to the dried master batch, and the extrusion process was performed again. The extrusion conditions at this time are:
The resin temperature was 260 ° C., the screw rotation speed was 500 rpm, and the residence time was about 2 minutes. In Comparative material No. to which no polyurethane resin was added. Extrusion was performed again for 16a in order to make the heat history the same.

A notched Izod impact test (according to JIS K 7110) was conducted at room temperature, and the evaluation contents are shown in Table 16. From the results in Table 16, it can be seen that even in the alloy type resin, the Izod impact value is improved by adding a combination of talc as a solid filler and a crosslinked polyurethane resin, and the composite resin of the present invention improves mechanical properties. It turns out to be effective.

[0102]

[Table 16] (Example 9) In Example No. 9 which is a composite resin of an alloy resin-based resin. 20 and Comparative Example No. 20. The phase structure was observed with a transmission electron microscope (TEM) using the untested test piece of 16a.

Example No. FIG. 5 (a) shows a TEM observation photograph of No. 20, and FIG.
o. FIG. 6A shows a TEM observation photograph of 16a, and FIG. The comparative example No. of the photograph FIG.
16a shows that talc 1 as a solid filler is present in the non-reactive resin (homo-PP resin matrix and rubber particles 3).

On the other hand, in Example No. of FIG. 2
In the case of 0, the crosslinked polyurethane resin hydrolysis product 2 is aggregated so as to cover the talc 1 as the solid filler, and it is understood that the solid filler is a crystal nucleus. According to this TEM observation, Example No. In No. 20, it was found that the hydrolysis product of the crosslinked polyurethane resin was aggregated on the rubber phase side of the interface between the rubber phase 3 and the resin phase.

Next, a differential scanning calorimeter (DSC)
Using Example No. 20 and Comparative Example No. The melting point temperature and the crystallization start temperature of 6a (100% homo PP resin) and Comparative Example 16a (the same resin composition as in Example 20 except that the treatment material 1 was not included) were measured. The evaluation sample was cut out from a non-evaluated test piece produced by injection molding and used. Table 17 shows the details of the evaluation.

Comparative Example No. The crystallization onset temperature of Comparative Example No. 16 of the homo PP resin was due to the nucleus effect of talc. 6
6 ° C. higher than “a”. On the other hand, in Example No. In Comparative Example No. 20, It can be seen that the crystallization start temperature has dropped to the level of 6a, and that the talc nucleus material effect has been lost. This also indicates that the hydrolysis product of the crosslinked polyurethane resin is agglomerated using talc as a core material.

[0107]

[Table 17] (Example 10) Example N which is an alloy resin-based composite resin
o. 17 and Comparative Example No. 17 A tensile test was performed using the test piece 13a, and the phase structure of the crazing (whitening) portion was observed with a transmission electron microscope (TEM). The tensile test was in accordance with JIS K7161 and JIS K7162.

From the TEM observation, it was found that Example No. In No. 17, many microcrazes occurred, and it was found that these microcrazes absorbed deformation energy. On the other hand, Comparative Example No. containing no crosslinked polyurethane resin hydrolysis product.
In the case of 13a, it was found that the amount of generated microcraze was smaller than that of the example product. Next, in Example No. 17 and Comparative Example No. 17 Using the test piece after the tensile test of 13a, the structure of the crazing (whitening) portion was observed by a scanning electron microscope (SEM).

Example No. FIG. 7 (a) shows an SEM observation photograph of Comparative Example No. 17. The SEM observation photograph of 13a is shown in photograph 8 (a). Example No. In FIG. 7 (a), a number of microvoids (pupil phenomena) 6 are generated as shown in the schematic diagram of FIG. 7 (b), and it can be seen that the microvoids 6 absorb deformation energy.

On the other hand, Comparative Example No. containing no hydrolysis product of the crosslinked polyurethane resin. Photograph 13a of FIG. 8 (a)
As shown in FIG. 8B, the amount of microvoids generated is smaller than that of the product of the present invention. Note that FIG. 8 shows that the magnification is about twice that of FIG. 7 and that the number of microvoids 6 is small. Example N
o. 17 shows that the hydrolysis product phase of the crosslinked polyurethane resin serves as a starting point, increases microvoids (pupil phenomenon) and microcraze, absorbs deformation energy, and improves mechanical properties.

Example 11 Using the test piece after the tensile test, the specific gravity of the crazing (whitening) portion was measured, and the retention when the initial specific gravity was set to 100 was measured. As a measurement sample, a non-reactive resin homo-PP resin (H501), talc and a PU resin in a natural moisture absorption state (moisture absorption: about 0.8%) were used. 21 and Example No. 22 and Comparative Example No. 22. 7a and 10a were produced. Each composition ratio is
It is shown in Table 18.

The examples and comparative examples were produced by using the twin screw extruder of the above-mentioned apparatus 3, pulled into strands, and pelletized and taken out. Next, the pellets were subjected to a drying treatment, and test pieces were prepared by injection molding, which were used as evaluation materials. In the extrusion process, the homo PP resin, talc, and the treatment material 3 were measured and mixed, and were simultaneously kneaded. The extrusion treatment conditions were a resin temperature of 260 ° C., a screw rotation number of 500 ppm, and a residence time of about 2 minutes. The resin temperature at this time is not lower than the molten resin of the non-reactive resin and not lower than the hydrolysis temperature of the crosslinked polyurethane resin. The injection molding conditions were a resin temperature of 190 ° C. and a mold temperature of 60 ° C.

Table 19 shows the retention ratio when the initial specific gravity of the crazing (whitening) portion of the example and the comparative example was set to 100.
Shown in As shown in Table 19, in the combination of talc (solid filler) and the crosslinked polyurethane resin hydrolysis product, the rate of decrease in specific gravity with respect to the amount of displacement was larger than in the comparative example, and many microcrazes and microvoids were generated. You can see that it was done.

This example shows that the hydrolysis product phase of the crosslinked polyurethane resin serves as a starting point, increases microvoids (pupil phenomenon) and microcraze, absorbs deformation energy, and improves mechanical properties.

[0115]

[Table 18]

[0116]

[Table 19] (Example 12) Homo PP resin (H501), EPR (V
0115), the melt viscosity at 240 ° C. of the hydrolysis product of EBR (N0372) and PU resin (treatment material 4) was measured using a Koka type flow tester, and the evaluation results are shown in Table 20.

From the results shown in Table 20, the melt viscosity of the hydrolysis product of PU resin is significantly lower than that of other resin materials.
It turns out that it is easy to aggregate around the filler. The measured temperature in this example is 240 ° C., which is higher than the resin viscosity during injection molding (about 200 ° C.), but it can be determined that there is no difference in the relative change in the melt viscosity. Also, homo PP resin, E
It has been found that in a combination of PR and EBR, when a rubber having a lower melt viscosity than that of the homo PP resin is used, the filler moves to the rubber phase.

[0118]

[Table 20] (Example 13) A non-reactive resin homo PP resin (H50
Example No. 1) using talc as a solid filler and PU resin (treated material 3) in a natural moisture absorbing state (moisture absorption: about 0.8%) and a hydrolysis product of PU resin (treated material 4) . 1
1 and Example No. 1. 23 to 25 and Comparative Example Nos. 8a was produced. Table 21 shows each composition ratio. Table 12 shows the compounding method of the PU resin and the conditions of the extrusion treatment. In addition, the injection molding conditions in this embodiment are as follows: resin temperature 190 ° C., mold temperature 60 ° C.
° C.

Example No. 11 and Example No. 23 and Comparative Example No. 8a was produced using the twin-screw extruder of the above-mentioned apparatus 3, pulled into a strand, and then pelletized and taken out. Next, the pellets were subjected to a drying treatment, and test pieces were prepared by injection molding, which were used as evaluation materials. In the extrusion treatment, the homo PP resin, talc, the treatment material 1 or the treatment material 4 were measured and mixed, and were simultaneously kneaded.

The resin temperature during the extrusion treatment in the examples is not lower than the temperature of the molten resin of the non-reactive resin and not lower than the hydrolysis temperature of the crosslinked polyurethane resin. Example No. The resin temperature during the extrusion process of No. 23 is equal to or higher than the melting temperature of the non-reactive resin.
Example No. 24 and Example No. 24. In No. 25, a homo-batch resin and talc were weighed and mixed using a twin-screw extruder of the processing apparatus 3, and kneading (resin temperature 190 ° C.) was simultaneously performed by an extruder to prepare a master batch.

Next, a predetermined amount of the PU resin or a hydrolysis product of the PU resin was added to the dried master batch, and the extrusion treatment was performed again. Example No. The resin temperature during the extrusion process of No. 24 is not lower than the molten resin temperature of the non-reactive resin and not lower than the hydrolysis temperature of the crosslinked polyurethane resin.

Example No. The resin temperature during the re-extrusion treatment of No. 25 is equal to or higher than the molten resin temperature of the non-reactive resin. Notched Izod impact test at room temperature (JIS K7110
Table 23 shows the evaluation contents. Example 23 of Table 23. 11 and Example No. 23 to Example No. 23. The results up to 25 indicate that the present invention is effective for improving mechanical properties.

[0123]

[Table 21]

[0124]

[Table 22]

[0125]

[Table 23]

[0126]

The composite resin of the present invention is softened by breaking the bonding points due to heat, hydrolysis, exchange reaction and the like added to the crosslinked polyurethane resin in the reactive resin to be mixed, and becomes finer by shearing force. And at the same time, the crosslinking with the reactive resin proceeds to form a copolymer. Therefore, the composite resin can be more uniformly dispersed in the reactive resin than in the case where the crosslinked polyurethane resin powder is simply added, and the resin properties similar to the graft resin can be modified.

Further, when the crosslinked polyurethane resin powder and the non-reactive resin are kneaded under hydrolysis conditions, the bonding points of the crosslinked polyurethane resin are cut by the hydrolysis and softened, and the non-reactive resin and the non-reactive resin are finely divided by the shearing force. And uniform. Furthermore, even when the non-reactive resin has a polar group, the interaction between the urethane bond and the polar group enhances the compatibility in the resin and can suppress a decrease in physical properties. So, simply,
An excellent effect as a filler can be exhibited as compared with the case where a mechanically pulverized material is added.

Even if coarse particles larger than 1 mm are used, the crosslinked polyurethane resin powder has a reaction or compatibility with the thermoplastic resin as described above, and can be dispersed as fine particles in the resin by shearing force. As described above, by finely dispersing and softening the crosslinked polyurethane resin, the surface quality and fracture resistance of the composite resin are improved. The main bond of the crosslinked polyurethane resin is a urethane bond and a urea bond, and the sub bonds are an allophanate bond and a burette bond. Reactive groups generated by hydrolysis of the crosslinked polyurethane resin are an amino group and a hydroxyl group.

It is estimated that the compatibility between the polyurethane resin in which the rubber component in the alloy resin is finely dispersed and the thermoplastic resin is improved. Further, when the alloy resin is kneaded at an oxidation temperature or higher, it is presumed that an active group such as a carboxyl group is generated and chemically bonded to the polyurethane resin. Therefore, since the polyurethane resin is no longer the starting point of the defect, the mechanical properties are improved.

When the composite resin contains a solid filler,
The solid filler acts as a coagulation nucleus material for the crosslinked polyurethane resin hydrolysis product, resulting in a structure surrounded by the crosslinked polyurethane resin hydrolysis product. Thereby, fine dispersion of the crosslinked polyurethane resin in the non-reactive resin can be expected. Also, when the molded article of the composite resin is deformed, the interface between the fine particles of the hydrolysis product of the crosslinked polyurethane resin and the non-reactive resin (or an alloy resin thereof) is separated,
A minute void (pupil phenomenon) is generated to absorb deformation energy. Furthermore, since the interface serves as a starting point of microcraze, deformation energy can be absorbed. By this action, the mechanical properties of the composite resin molded article are improved.

Further, the hydrolysis product of the crosslinked polyurethane resin aggregates or disperses at the interface between the rubber of the alloy resin and the resin to serve as a starting point of microcrazing, and it is expected that the mechanical properties of the composite resin molded article will be improved.

[Brief description of the drawings]

FIG. FIG. 2 is a scanning electron micrograph showing a dispersion state of crosslinked polyurethane resin particles in a resin cross section of Composite No. 1.

FIG. FIG. 3 is a scanning electron micrograph showing the dispersion state of crosslinked polyurethane resin particles in the resin cross section of the composite of FIG. 1a.

FIG. 6 is a scanning electron micrograph showing a dispersion state of crosslinked polyurethane resin particles in a resin cross section of the composite of No. 6.

FIG. FIG. 5 is a scanning electron micrograph showing the dispersion state of crosslinked polyurethane resin particles in the resin cross section of the composite of 2a.

FIG. 5 (a) Example No. 20 is a transmission electron micrograph showing a dispersion state of talc and crosslinked polyurethane resin particles in a resin cross section of the composite of No. 20. FIG. (B) Figure (a)
FIG.

6 (a) Comparative Example No. FIG. 16 is a transmission electron micrograph showing a dispersion state of talc in a resin cross section of the composite of FIG. 16a. (B) It is a schematic explanatory view of FIG.

FIG. 7 (a) Example No. 17 is a scanning electron micrograph of the tissue structure of the crazed portion of the test piece after the tensile test of No. 17. FIG. (B) It is a schematic explanatory view of FIG.

8 (a) Comparative Example No. 17A is a scanning electron micrograph of the tissue structure of the crazing portion of the test piece after the tensile test of 17a. (B) It is a schematic explanatory view of FIG.

[Explanation of Codes] Talc, 2. 2. PU hydrolysis products; Rubber particles 6. Micro void

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 11/28 C08J 11/28 C08K 3/00 C08K 3/00 C08L 23/00 C08L 23/00 75/04 75/04 101/00 101/00 (72) Inventor Takumi Taniguchi 41-Cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture 1 Toyota Toyota Central Research Laboratory Co., Ltd. (72) Inventor Takashi Ota Nagakute-cho, Aichi-gun, Aichi Prefecture (71) Inventor Norio Sato, No. 41, Toyota Central Research Institute, Inc. (72) Inventor Norio Sato No. 41, Toyota Chuo Research Institute, Inc. (72) Inventor, Yuji Hoshino 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Co., Ltd. (72) Inventor Kanemitsu Kondo 1 Toyota Town Toyota City, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Invention Nariaki Abe 1 Toyota Town, Toyota City, Aichi Prefecture, Toyota Motor Corporation (72) Inventor Toshiyuki Suzuki 1 Toyota Town, Toyota City, Aichi Prefecture, Toyota Motor Corporation

Claims (18)

[Claims] 1. A crosslinked polyurethane resin and a reactive resin,
A resin obtained by at least reacting the partially cross-linked polyurethane resin obtained by kneading at a temperature higher than the melting temperature of the reactive resin and partially hydrolyzed and having at least half of the urethane bonds cut, and the reactive resin. A composite resin characterized by the above. 2. The composite resin according to claim 1, wherein said reactive resin is a thermoplastic resin having at least one of ester group, carboxyl group, acid anhydride group, amino group, hydroxyl group and oxazoline group. 3. The composite resin according to claim 1, wherein the reactive resin is a polyamide resin or an alloy resin containing a polyamide resin. 4. The modified crosslinked polyurethane resin according to claim 1, wherein the hydroxyl compound (hydroxyl group-containing compound), the isocyanate group-containing compound, and the crosslinking agent are semi-rigid or rigid urethane resins obtained by reaction injection molding. Composite resin. 5. A modified crosslinked resin obtained by kneading a crosslinked polyurethane resin and a non-reactive resin at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin, wherein a part thereof is hydrolyzed and at least half of urethane bonds are cut. A composite resin, which is a mixture of a polyurethane resin and the non-reactive resin. 6. The composite resin according to claim 5, wherein said non-reactive resin is an olefinic thermoplastic resin. 7. A part obtained by kneading a crosslinked polyurethane resin and an olefin-based thermoplastic alloy resin at a temperature not lower than the hydrolysis temperature of the crosslinked polyurethane resin is partially hydrolyzed and at least half of urethane bonds are cut. A composite resin, which is a mixture of an altered crosslinked polyurethane resin and the olefin-based thermoplastic alloy resin. 8. The composite resin according to claim 7, wherein the olefin-based thermoplastic alloy resin is an olefin-based thermoplastic resin containing an olefin-based rubber elastic body. 9. A method in which a solid filler is used as a nucleus in a matrix of the non-reactive resin or the olefin-based thermoplastic alloy resin containing an olefin-based rubber elastic body, the resin having a relatively high viscosity at the time of melting. A composite resin characterized in that a hydrolysis product of a crosslinked polyurethane resin having a relatively low resin viscosity is dispersed in fine particles. 10. The composite resin according to claim 9, wherein said non-reactive resin is an olefin-based thermoplastic resin. 11. The composite resin according to claim 9, wherein said olefin-based thermoplastic resin is a polypropylene resin. 12. The olefin-based thermoplastic alloy resin comprises:
The composite resin according to claim 9, which is an olefin-based thermoplastic resin containing an olefin-based rubber elastic body. 13. The composite resin according to claim 9, wherein said relatively low viscosity non-reactive resin is a hydrolysis product of a crosslinked polyurethane resin. 14. The crosslinked polyurethane resin hydrolysis product is a hydrolyzate containing a hydroxy compound, an isocyanate compound and a crosslinker obtained by reaction injection molding of the crosslinked polyurethane resin, and partially maintains crosslinkage. The composite resin according to claim 9, which is cut and partially cut. 15. The composite resin according to claim 9, wherein the hydrolysis product of the crosslinked polyurethane resin is a fine particle having a particle size of 200 μm or less. 16. The composite resin according to claim 9, wherein said solid filler has a particle size of 100 μm or less. 17. The talc according to claim 9, wherein said solid filler is talc.
The composite resin according to item 1. 18. The composite resin according to claim 9, wherein the weight ratio of the hydrolysis product of the crosslinked polyurethane resin to the solid filler is in the range of 5: 1 to 1:20.