JP3348512B2 - Modifier and method for modifying thermoplastic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modifier and a method for modifying a thermoplastic resin. More specifically, the present invention relates to a thermoplastic resin modifier which is excellent in storage stability at room temperature and initiates a crosslinking reaction under elevated temperature or other controlled conditions, and a method for modifying a thermoplastic resin using the same. .

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been improved in water resistance, heat resistance, abrasion resistance, oil resistance, chemical resistance, weather resistance, adhesion, impact resistance, etc. by a crosslinking reaction with an isocyanate compound or the like. This is a known fact. However, the isocyanate compound generally has a high reactivity with the active hydrogen compound because the isocyanate group is highly reactive. Therefore, even if the isocyanate compound is stored alone, it reacts with moisture in the air to lower the isocyanate group concentration. To prevent this, it must be replaced with an inert gas, sealed and stored. In addition, after the isocyanate compound is added to the resin to be modified, the viscosity increases due to crosslinking and / or polymerization with the lapse of time even at room temperature. Therefore, the isocyanate compound has been used as a two-pack type that is mixed with the base agent immediately before use. However, in the case of the two-pack type, in addition to the trouble of the mixing process, there are problems such as uneven mixing and variation in physical properties of the product resulting from weighing errors. In order to solve these problems, it has been attempted to add a blocked isocyanate compound.

[0003]

However, in the method using such a blocked isocyanate compound as a modifier, appearance properties such as roughening of a crosslinked product and foaming due to the dissociated blocking agent flying out of the system. However, there is a problem in that the working environment is deteriorated due to a decrease in the amount of white smoke and the like, and furthermore, there is a problem such as contamination of the processing machine. Therefore, it is necessary to avoid or reduce the use of such a blocking agent. In other words, there has been a strong demand for a thermoplastic resin modifier that does not generate scattered substances that adversely affect the environment during the reaction and has high storage stability at room temperature. The present invention has excellent storage stability without reacting even if it is blended with a thermoplastic resin to be stored or modified alone at room temperature or slightly higher temperature, and has excellent storage stability. It is an object of the present invention to provide a thermoplastic resin modifier in which the uretdione group starts to react under the conditions controlled by the above, and a method for modifying the thermoplastic resin using the modifier, such as durability.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve such conventional problems, and as a result, they have no free isocyanate group in the molecule but generate an isocyanate group by heat. The present inventors have found that a compound into which a uretdione group and an isocyanurate group are introduced has semipermanent storage stability and can improve the durability and the like of a thermoplastic resin, and have completed the present invention.

That is, according to the present invention, there is provided a thermoplastic resin modifier characterized by containing a compound having at least a uretdione group and an isocyanurate group in a molecule and having an active hydrogen group at a molecular chain terminal. Provided.

According to the present invention, there is further provided a method for modifying a thermoplastic resin, comprising mixing the modifier with a thermoplastic resin and heating the mixture to react the uretdione group of the modifier.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

First, the compounds contained in the modifier of the present invention will be described in detail. The compound comprises a polyisocyanate component (a) and an active hydrogen compound component (b) having an equivalent ratio of active hydrogen groups in the active hydrogen compound component (b) to isocyanate groups in the polyisocyanate component (a). It has at least a uretdione group and an isocyanurate group in the molecule, and has an active hydrogen group at a molecular chain terminal, which is obtained by reacting under an active hydrogen group excess condition exceeding 1.0. The condition for excess of the active hydrogen group in the active hydrogen compound component (b) relative to the isocyanate group in the polyisocyanate component (a) is necessary in order for the compound to be produced to contain active hydrogen groups without leaving any isocyanate groups. In practice, the average number of isocyanate groups in the polyisocyanate component (a) due to the isocyanurate group content and the average number of active hydrogen groups in the active hydrogen compound component (b) due to the introduction of triol, etc. It is important to determine conditions that do not cause gelation, to mix them so as to satisfy these conditions, and to carry out the reaction while maintaining the temperature below the temperature condition at which the uretdione group opens. The compounding ratio is described in J.
P. According to the gelation theory theoretically calculated by Flory, Khun et al., In practice, the reaction is carried out at a compounding ratio taking into account the reactivity ratio of the reactive groups contained in the component (a) and (b) component molecules. By doing so, the compound can be produced without gelation. The compound is in a molten state, a bulk state, or, if necessary, an inert solvent commonly used in the polyurethane industry, for example, an aromatic hydrocarbon solvent such as toluene or xylene, an ethyl acetate, an ester solvent such as butyl acetate, or methyl ethyl ketone. , Ketone solvents such as cyclohexanone, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate,
Use one or more of glycol ether ester solvents such as ethyl-3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, and polar solvents such as dimethylformamide, dimethylacetone, N-methylpyrrolidone, and furfural. And in a solution state, temperature conditions at which the uretdione group does not open the ring, preferably 100
It can be manufactured by uniformly mixing and reacting each component at a temperature of not more than 0 ° C. within the above-mentioned mixing condition range. As a reactor,
Any device can be used as long as the above-mentioned homogeneous reaction can be achieved.
For example, a mixing and kneading apparatus such as a reaction vessel or a kneader equipped with a stirrer, a single-screw or multi-screw extrusion reactor, or the like can be used. In order to accelerate the reaction, a metal catalyst such as dibutyltin dilaurate or a tertiary amine catalyst such as triethylamine which is commonly used in the production of polyurethane resin can be used as a catalyst. Depending on the polyisocyanate component (a) or active hydrogen compound component (b) used, the compound thus produced may be a urethane group, a urea group, a carbodiimide group, in addition to a uretdione group, an isocyanurate group and an active hydrogen group. , A uretonimine group, an oxazolidone group, a hydantoin group, or other group derived from an isocyanate group, but containing substantially no isocyanate group, and a uretdione group and an active hydrogen group. = 0.40 to 1.00, preferably 0.45 to 0.95. In particular, a compound having a urethane group in addition to a uretdione group, an isocyanurate group and an active hydrogen group in a molecule, that is, a polyurethane resin having a uretdione group and an isocyanurate group in a molecule and having an active hydrogen group at a molecular chain terminal is preferable. The number average molecular weight of such a polyurethane resin is preferably 500 or more, more preferably 2,000.
A range of from 50,000 to 50,000 is particularly preferred.

The polyisocyanate component (a) contains at least one uretdione group and an isocyanurate group in the molecule, and optionally contains one or two groups other than these two groups derived from the isocyanate group. It comprises at least one kind of polyisocyanate compound (a1) and, if desired, one or more kinds of polyisocyanates (a2) containing two or less isocyanate groups in the molecule. Examples of the group other than the uretdione group and the isocyanurate group derived from the isocyanate group of the polyisocyanate compound (a1) include a urethane group, a urea group, a carbodiimide group, a uretonimine group, an oxazolidone group, and a hydantoin group. Examples of the polyisocyanate for forming the polyisocyanate compound (a1) include a monomer of a free polyisocyanate and a polymer thereof. Examples of the polyisocyanate monomer include 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI), 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, ,
4'-diphenylmethane diisocyanate (hereinafter MDI
, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-
Diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-
Diisocyanate, 3,3'-dimethoxydiphenyl-
Aromatic diisocyanates such as 4,4'-diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, water Reaction of a diisocyanate such as an alicyclic diisocyanate such as an added xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or tetramethyl xylene diisocyanate, or a reaction of the polymer of the diisocyanate or a bifunctional or higher polyol with the diisocyanate or a polymer thereof. Can be mentioned. Both the polymer of polyisocyanate and the polyol adduct of polyisocyanate are particularly suitable. In any case, the polyisocyanate compound (a1) may contain at least a uretdione group and an isocyanurate group, and may be, for example, a mixture of a uretdione group-containing polyisocyanate compound and an isocyanurate group-containing polyisocyanate compound. Alternatively, a uretdione group and an isocyanurate group-containing polyisocyanate compound may be used. In general, these are formed by a dimerization reaction (uretdionation reaction) and a trimerization reaction (isocyanuration reaction) of a polyisocyanate (monomer), and can be specifically produced, for example, as follows.

That is, such a mixture is prepared from one or more corresponding polyisocyanates (monomers) to known uretionation catalysts such as triethylphosphine, dibutylethylphosphine, tributylphosphine, tri-n-propylphosphine. 0 to 90 ° C. in the presence of trialkylphosphines such as triamylphosphine, tribenzylphosphine and the like or pyridine and the like.
At a reaction temperature of no solvent or an inert solvent commonly used in the polyurethane industry, for example, an aromatic solvent such as toluene and xylene, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, and an ester solvent such as ethyl acetate and butyl acetate. In the presence of a solvent, a glycol ether ester-based solvent such as propylene glycol methyl ether acetate, ethyl-3-ethoxypropionate, or in some cases, in a plasticizer such as a polyol or dioctyl phthalate (DOP) which is liquid at the reaction temperature. Can be manufactured. The reaction solution contained 2% of its isocyanate group content.
When 0 to 50 mol% of the isocyanate groups have reacted,
For example, a solution of phosphoric acid, methyl p-toluenesulfonate, sulfur or the like is added to inactivate the uretdionation catalyst and stop the reaction. Depending on the type of polyisocyanate to be used, some of the polyisocyanates become crystals and precipitate during this reaction. In particular, aromatic polyisocyanates generally crystallize,
Separate from the reaction system. By such a method, a uretdione group-containing polyisocyanate compound (that is, a dimer or a poly-uretdione compound), and a uretdione group and an isocyanurate group-containing polyisocyanate compound,
A mixture of the isocyanurate group-containing polyisocyanate compound and the raw material polyisocyanate monomer is produced. By removing the raw material polyisocyanate monomer from the mixture by thin-film distillation or the like, the desired polyisocyanate compound (a1) such as a polyisocyanate compound containing a uretdione group and an isocyanurate group can be obtained. The higher the temperature of the reaction during the production and the lower the content of the polyisocyanate monomer when the reaction is stopped, the higher the ratio of isocyanurate groups formed. Further, as the amount of the catalyst such as triethylphosphine is larger, the generation ratio of the uretdione group is higher. By controlling these reaction conditions, a polyisocyanate compound containing a specific ratio of uretdione groups and isocyanurate groups can be obtained. The uretdione group content of the polyisocyanate compound (a1) thus obtained is preferably from 8 to 25% by weight, particularly preferably from 10 to 23% by weight, and the isocyanurate group content is from 1 to 24% by weight, particularly from 3 to 24% by weight. 20% by weight is preferred. In addition, HDI is particularly suitable as a polyisocyanate constituting the polyisocyanate compound (a1) because it is non-yellowing and is liquid at a solid content of 100% by weight. JP-B-1-50265, JP-B-2-1633
No. 2, JP-A-58-37022, the amount of the dimer polymer is limited as much as possible even when the polyisocyanate contains only a pure dimer or a polymer thereof. In particular, the incorporation of an isocyanurate group that gives a branched structure is avoided as much as possible because the compound contained in the modifier of the present invention gels during production. On the other hand, when the isocyanurate group as well as the uretdione group is positively introduced into the molecule as in the polyisocyanate component (a) of the present invention,
Excellent heat resistance and durability.

The polyisocyanate (a2) optionally used is a compound containing not more than two isocyanate groups in the molecule among the polyisocyanates for forming the polyisocyanate compound (a1) already exemplified. These (a1) and (a2) may be of the same type or different types.
When the type of the polyisocyanate (a2) is the same as the type of the polyisocyanate for forming the polyisocyanate compound (a1), the polyisocyanate compound (a1) containing an unreacted polyisocyanate monomer may be used as it is in the present invention. Can be used as the polyisocyanate component (a), which is the main raw material component. An uretdione group- and isocyanurate group-containing polyisocyanate compound or the like, excluding unreacted polyisocyanate monomer, is mixed with a polyisocyanate monomer, and the polyisocyanate component (a) having a reduced number of functional groups is converted into an active hydrogen compound component ( The reaction with b) may be preferable without causing a problem such as gelation at the time of the reaction, and may be effective in controlling the reactivity and the properties of the expressed substance. The isocyanate group equivalent ratio of the polyisocyanate compound (a1) excluding the unreacted polyisocyanate monomer and the polyisocyanate (a2) is as follows:
The polyisocyanate (a2) / polyisocyanate compound (a1) is preferably selected from 0 to 5.70, particularly preferably 0.10 to 4.00, and more preferably 0.1 to 4.00.
5-3.00 is most desirable.

The active hydrogen compound component (b) contains one or more active hydrogen groups in the molecule. Specifically, besides water, those containing one or more selected from polyols, amino group-containing polyamines, urea resins, melamine resins, epoxy resins, polyester resins, acrylic resins, polyvinyl alcohol, and the like are included. preferable. Particularly, polyol is preferable. Polyols known in the polyurethane industry can be used as the polyol, and the polyisocyanate component (a)
In the above, since the isocyanate group has two or more functional groups, a polyol having a low functional group number such as a bifunctional group is suitable for preventing gelation during the reaction. Examples of the polyol include polyester polyol, polyester amide polyol, polyether polyol, polyether / ester polyol, polycarbonate polyol and the like. Specifically, for example, a known succinic acid,
Dicarboxylic acids such as adipic acid (hereinafter abbreviated as AA), sebacic acid, azelaic acid, terephthalic acid (hereinafter abbreviated as TP), isophthalic acid (hereinafter abbreviated as IP), hexahydroterephthalic acid, and hexahydroisophthalic acid;
These acid esters, acid anhydrides, etc., ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol (hereinafter abbreviated as 1,2-PG), 1,4
-Butylene glycol (hereinafter abbreviated as 1,4-BG), 1,5-pentane glycol, 1,6-hexane glycol (hereinafter abbreviated as 1,6-HG), 3-methyl-1,5-pentane glycol , Neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol , 2, 2
-Diethyl-1,3-propanediol, 1,8-octaneglycol, 1,9-nonanediol, diethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, trimer Methylolpropane (hereinafter abbreviated as TMP), glycerin, hexanetriol, N, N,
Glycols such as N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or ethylene oxide or propylene oxide adduct of bisphenol A, or diamines such as hexamethylenediamine, xylenediamine, isophoronediamine, monoethanolamine, isopropanoltriamine And polyesteramines and polyesteramide polyols obtained by a dehydration-condensation reaction with triamine or amino alcohol alone or a mixture thereof. Further, ε-caprolactone, alkyl-substituted ε-caprolactone, δ-
There are polyester polyols such as lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (that is, lactone) monomers such as valerolactone and alkyl-substituted δ-valerolactone. Examples of the polyether polyol include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol, and the like. Examples of the polyether / ester polyol include those produced from the above polyether polyol and the above dicarboxylic acid or acid anhydride. Polycarbonate polyol is obtained, for example, from the reaction of hexane glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexane dimethanol and the like with diethyl carbonate, diphenyl carbonate and the like. N-980 and N-981 manufactured by Co., Ltd., and the like. Further, the monomolecular diols and triols mentioned as the raw materials of the polyester polyol, that is, ethylene glycol, 1,3-propylene glycol, 1,2-P
G, 1,4-BG, 1,5-pentane glycol, 1,
6-HG, 3-methyl-1,5-pentane glycol,
Neopentyl glycol, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol,
Cyclohexane-1,4-diol, cyclohexane-
1,4-dimethanol, dimer acid diol, TMP,
Glycerin, hexanetriol, N, N, N ', N'
-Tetrakis (2-hydroxypropyl) ethylenediamine or an ethylene oxide or propylene oxide adduct of bisphenol A can also be used as the polyol. Examples of polyamines containing amino groups include monomolecular diamines, triamines, aromatic diamines,
And polyether polyamines in which the terminal of the polyether is an amino group. In addition, urea resins, melamine resins, epoxy resins, polyester resins, acrylic resins, polyvinyl alcohols, and the like are generally known in the polyurethane industry, and if they contain two or more active hydrogen groups, the active hydrogen compound component (b ) Can be used as all or a part. As monofunctional hydroxy compounds, glycidol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate,
Hydroxypropyl methacrylate and the like. These active hydrogen compound components (b) may be water or have a molecular weight of 6
Preferred are those of 2 to 20,000, and more preferred are 62 to 500.
A value of 0 is particularly preferred. If the molecular weight is too large, the amount of the uretdione group, isocyanurate group, urethane group, urea group, and the like to be introduced decreases, and the effect of modifying the added resin is undesirably reduced.

The thermoplastic resin modified in the present invention includes, for example, polychloroprene rubber, 1,2-polybutadiene, 1,4-polybutadiene, polyethylene,
Polypropylene, styrene-butadiene resin, vinyl acetate resin, acrylonitrile-butadiene resin, vinyl chloride resin, vinyl chloride-vinyl acetate resin, polyurethane resin (polyurethane polyol, polyurea polyol, polyurethane urea polyol, etc.), polyamide resin, epoxy resin, polyamine , Urea resin, melamine resin, phenol resin, unsaturated polyester resin, saturated polyester resin, polyacetal resin, epoxy group-containing acrylic resin, polyvinyl alcohol, polyester polyol, polyacryl polyol, polyether polyol, and copolymers or mixtures thereof And polyurethane resins (polyurethane polyols, polyurea polyols, polyurethane urea polyols). And the like), saturated polyester resin,
Polyacryl polyol, vinyl chloride resin, vinyl chloride-vinyl acetate resin, polyacetal resin, and polypropylene are suitable, and may be in any of a liquid state and a solid state. Further, it may contain a solvent or water.

The thermoplastic resin modified in the present invention may contain other substances as required, such as an antioxidant, an ultraviolet absorber, a heat resistance improver, a coloring agent, an inorganic or organic filler, and a plasticizer. , A lubricant, an antistatic agent, a reinforcing material, a silane coupling agent, a uretdione group dissociation catalyst, and the like.

The amount of the modifying agent of the present invention depends not only on the content and molecular weight of the uretdione group and the isocyanurate group of the modifying compound but also on the thermoplastic resin to be modified. It is necessary to select an appropriate amount depending on the functional group concentration, molecular weight, properties and degree to be modified, etc., but about 5 to 40 parts by weight (as a solid content) is suitable for 100 parts by weight of the thermoplastic resin. .

The method of mixing the modifying agent of the present invention and the thermoplastic resin to be modified takes an appropriate mixing method depending on the state of both, for example, solid or liquid under normal conditions, melt viscosity, etc. be able to. Specific mixing methods include mixing in a container, dry blending, kneading with a twin-screw extruder or a kneader, and the like. After the modifier is mixed with the thermoplastic resin, the uretdione group is cleaved to form an isocyanate group, and then heated to a temperature at which it reacts with active hydrogen groups in the system, for example, at 110 to 250 ° C. to effect crosslinking.

[0017]

Next, the present invention will be described in detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto. Parts and% in the synthesis examples, examples and comparative examples are in principle “parts by weight” and “% by weight”, respectively.
Means The uretdione group content and the isocyanurate group content in the synthesis examples are obtained by converting each functional group into an isocyanate group content.

[Synthesis of Modifier Compound] Synthesis Example 1 A polyisocyanate compound derived from HDI [isocyanate group content = 21.1%] was placed in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a cooler. Uretdione group content = 16.4%, isocyanurate group content = 12.5
% (Hereinafter abbreviated as polyisocyanate compound A)] 1
Then, 3-methyl-1,5-pentane adipate diol (having a hydroxyl value of 22) was prepared.
3) 236.5 parts were added and reacted at 75 ° C. Five hours later, the obtained polyurethane resin was measured by FT-IR. As a result, the absorption peaks of the isocyanurate group and the uretdione group remained unchanged from those at the start of the reaction, the absorption peak of the isocyanate group disappeared, and the urethanization was completed. did. When the molecular weight of this polyurethane resin was measured by gel permeation chromatography, the number average molecular weight was 7,000. This polyurethane resin is PUD-
Set to 100.

Synthesis Example 2 In a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler, 100 parts of polyisocyanate compound A and HDI1 were added.
0.6 part was charged, and then 257.8 parts of polybutylene adipate diol (having a hydroxyl value of 205) were added, followed by reaction at 75 ° C. After 5 hours, the obtained polyurethane resin is
As measured by T-IR, the absorption peaks of the isocyanurate group and the uretdione group remained unchanged from those at the start of the reaction, the absorption peak of the isocyanate group disappeared, and the urethanization was completed. This polyurethane resin is PUD-20
Set to 0.

Synthesis Example 3 100 parts of polyisocyanate compound A and 10.6 parts of glycidol were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a cooler, and then polybutylene adipatediol (hydroxyl value 205) 257. Add 8 parts and add 7
The reaction was performed at 5 ° C. After 5 hours, when the obtained polyurethane resin was measured by FT-IR, the absorption peaks of the isocyanurate group and the uretdione group did not change from those at the start of the reaction, and the absorption peak of the isocyanate group disappeared.
Urethane conversion is completed. This polyurethane resin is PUD
-300.

[Storage stability after blending modifier] Nipporan 3127 (polyester polyurethane resin, solid content 30
% Solution, 300 parts of methyl ethyl ketone / toluene / cyclohexanone = 4.5 / 3.5 / 2 (weight ratio, manufactured by Nippon Polyurethane Industry), 20 parts of PUD-100 was added, and mixed until a homogeneous solution was obtained. This mixture is heated to 50 ° C
Was stored in a constant temperature dryer, and the change with time of the viscosity was measured.
Even after three months of aging, the rate of increase in viscosity was within 10%.

[Modification of Thermoplastic Polyurethane Resin by Addition of Modifier] Example 1 300 parts of Nipporan 3127 were added to PUD-100.
Was added and mixed until a homogeneous solution was obtained. Using this mixture, a film having a thickness of about 100 μm was produced. Film curing conditions are: room temperature × 10 minutes + 60 ° C × 15
Min + 180 ° C. × 10 minutes + 25 ° C. × 2 days. Each performance test was performed on this film. Table 1 shows the results.

Example 2 Nipporan 3117 (polyester polyurethane resin,
20 parts of PUD-200 was added to 300 parts of a solid content of 35%, methyl ethyl ketone solution (manufactured by Nippon Polyurethane Industry), and mixed until a homogeneous solution was obtained. Using this mixture, a film having a thickness of about 1
A 00 μm film was produced. Each performance test was performed on this film. Table 1 shows the results.

Comparative Example 1 Using Nipporan 3127, a film having a thickness of about 100 μm was produced under the same film curing conditions as in Example 1. Each performance test was performed on this film. Table 1 shows the results.

Comparative Example 2 Using Nipporan 3117, a film having a thickness of about 100 μm was produced under the same film curing conditions as in Example 1. Each performance test was performed on this film. Table 1 shows the results.

[Performance Test] (1) Tensile Properties The tensile properties of each film were measured according to JIS K6301. (2) Softening point 500 on a film punched with JIS No. 2 dumbbell
When the film was suspended in a hot air circulating drier with a load of g / cm ^{2 and} the temperature was increased at a rate of 10 ° C./min (starting to increase the temperature from room temperature), the film rapidly expanded or The cut temperature was defined as the softening point. (3) Gel fraction About 1 g of the film was extracted with methyl ethyl ketone in a cylindrical filter paper, and the weight remaining ratio of the extracted film was defined as the gel fraction. Specimen shape; thickness about 100 µm, length x width = 5 mm x 80
mm Extraction equipment; SOXTEC SYSTEM HT 10
43 (manufactured by tector) Extraction conditions: 5 hours boiling + 1 hour washing with refluxing solvent

[0027]

[Table 1]

[Modification of Vinyl Chloride Resin by Addition of Modifier] Example 3 100 parts of Lulon TH-300 (straight soft vinyl chloride resin, manufactured by Tosoh, containing 55 parts of a plasticizer) were mixed with PU.
10 parts of D-300 was added and dry blended. Thereafter, the mixture was kneaded using a heated two-roll machine to obtain a bare sheet. This sheet was formed into a sheet having a thickness of 1 mm by a press machine. The respective molding conditions are as shown below. 180 ° C. Kneading time: 5 minutes Press machine conditions Press temperature: 175 ° C. Primary press: 0 kg / cm ² × 7 minutes Secondary press: 180 kg / cm ² × 5 minutes cooling; 180 kg / cm ² × 10 minutes The performance of the obtained sheet is shown in Table 2. The hardness is JI
SK6301, tensile test is JIS K6723, heat aging test is JIS K6723 (120 ° C × 72 hours), oil resistance is JIS K6723 (70 ° C × 4 hours), and wear resistance is measured according to JIS K7204. Was.

Comparative Example 3 A sheet having a thickness of 1 mm was formed using Ryuron TH-300 under the same forming conditions as in Example 3. Table 2 shows the performance of the obtained sheet.

[0030]

[Table 2]

[0031]

【The invention's effect】

(1) Even after the modifier of the present invention is added to a thermoplastic resin, it has semipermanent storage stability from room temperature to around 50 ° C. (2) By adding the modifier of the present invention to a thermoplastic resin, the normal properties, heat resistance, solvent resistance, and durability such as abrasion resistance were improved. (3) It does not generate any environmentally harmful flying substances such as free polyisocyanate monomers and blocking agents, and is excellent in operability and safety.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/77-18/79 C08G 18/10 C08L 75/04-75/12 C08L 101/00-101 / Ten

Claims (2)

(57) [Claims] 1. A thermoplastic resin modifier comprising a compound having at least a uretdione group and an isocyanurate group in a molecule and having an active hydrogen group at a molecular chain terminal. 2. A method for modifying a thermoplastic resin, comprising mixing the modifier according to claim 1 with the thermoplastic resin and heating the mixture to react the uretdione group of the modifier.