JPH08217890A - Sheet-like resin molding improved in moisture permeability - Google Patents

Abstract

PURPOSE: To obtain a sheet-like molding capable of providing functions such as appearance, touch feeling and moisture permeability similar to these of natural products required for leather made of vinyl chloride, synthetic leather, artificial leather, etc. CONSTITUTION: This resin molding is obtained by kneading and melting urea- aldehyde resin powder or melamine-aldehyde resin powder containing >=80wt.% primary particles having <=2μm particle diameter and containing >=95wt.% complex particles in which associated bodies formed by association of the primary particles have 100μm particle diameter or their mixed powder or organic natural product powder containing >=95wt.% particles having <=100μm particle diameter with a thermoplastic resin and then, molding the melt into a sheet or film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel resin molded product. More specifically, urea-aldehyde resin powder or melamine-aldehyde resin powder or a mixed powder thereof is kneaded with a thermoplastic resin and melt-molded into a sheet or a film, which has improved moisture permeability. Regarding molded articles.

[0002]

2. Description of the Related Art In recent years, vinyl chloride leather, synthetic leather,
With the trend toward higher quality, artificial leather and the like are required to have the functions of natural leather, such as the calm and rich feel, moisture absorption / release and moisture permeability. Conventionally, the surface of vinyl chloride sheet, synthetic leather, etc. is coated with a finishing agent containing synthetic resin such as urethane resin, acrylic resin, etc. as a binder and natural product powder, silica, etc. Although it has been processed, this method gives a gloss, feel, and pattern similar to natural products, but in terms of function, it depends largely on the physical properties of the sheet body, and compared with natural products, only surface treatment That was not enough.

Recently, leather fiber powder or leather powder obtained by crushing leather scraps as natural product powder, collagen powder obtained by separating collagen in animal tissue, refining, heat-stabilizing, and pulverizing, crab, Chitin, chitosan powder obtained by purifying and crushing shells of shrimp and other crustaceans, keratin powder (wool powder) crushed using the keratin part of wool, and silk powder in which silk threads are finely mixed and mixed. Sheets or films have been proposed, and as a prior example thereof, for example, JP-A-62-256900,
63-10641, 63-21983, 63-112778, 63-15270.
No. 0, JP-A-1-197599 and the like. By mixing and mixing these natural product powders, a remarkable improvement effect is recognized in physical properties such as moisture absorption and desorption,
Although it was effective in terms of moisture permeability, it was extremely insufficient.

Urea-aldehyde resin powders or melamine-aldehyde resin powders have hitherto been used as delustering agents for paints and pigments for papers. KOSHO 51-12051
No. 51-13491, No. 52-1398.
No. 7, JP-A-52-47490, JP-A-48-8
There are JP-A-0653 and the like, but they describe only the effect of addition of the matte surface layer and imparting a velvety soft feeling as pigments. Examples of pigments for paper include JP-A-54-135893, JP-A-55-36231, and JP-A-56-131658. These are sheet or film-shaped resin moldings used for synthetic leather and the like. It is essentially different from the thing, and its addition effect is
The purpose of the present invention is different from that of the present invention because of its whiteness, opacity, and prevention of strikethrough during printing.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel sheet or film-shaped resin molded product in which the above problems of the prior art are improved and the moisture permeability is improved.

[0006]

[Means for Solving the Problems] As a result of various studies for achieving the above object, urea-aldehyde resin powder or melamine-aldehyde resin powder or a mixed powder thereof is kneaded with a thermoplastic resin at a specific ratio, The inventors have found that the desired effect of improving moisture permeability can be achieved by melt-molding into a sheet or film, and have completed the present invention.

The urea-aldehyde resin powder, the melamine-aldehyde resin powder or a mixed powder thereof used in the present invention contains 80% by weight or more of primary particles having a particle diameter of 2 μm or less, and they are associated with each other. A powder containing 95% by weight or more of aggregate particles having an aggregate particle diameter of 100 μm or less is preferable.

Particularly, commercially available primary particles having an average particle size of submicron to several microns for paper processing or paint addition form an aggregate, and apparently have a particle size of several microns to several tens of microns. Powders can be used.
Regarding specific particle morphology, primary particle powders of urea-aldehyde resin or melamine-aldehyde resin having a particle size of submicron to several microns are physically or chemically aggregated or associated with each other by an electron microscope or the like. The state in which the aggregates are observed can be observed, and the aggregates can be measured as the apparent particle size without the aggregates collapsing under the particle size measurement conditions using a Coulter counter or Microtrac.

Various manufacturing methods are known, and for example, a method according to Japanese Patent Publication No. 6-70116 can be mentioned. In order to improve the moisture permeability which is the object of the present invention, the average particle size of the primary particles is preferably 2 μm or less, more preferably 1 μm.
Or less, and more preferably 0.5 μm or less.
Further, it is preferable that the aggregate has an apparent particle size of from the particle size of the primary particles to about 100 μm, more preferably from the particle size of the primary particles to about 50 μm, further preferably of the primary particle size. It is required to have an apparent particle size from the particle size to about 20 μm. When the content of particles having an average particle diameter of 100 μm or more in the aggregate increases,
It is not preferable because it becomes difficult to disperse the thermoplastic resin in the thermoplastic resin, the moldability of the sheet-shaped molded article is extremely lowered, and the smoothness of the surface is impaired.

When a powder having primary particles not forming an aggregate structure and having a particle size of several microns to several tens of microns is used, the apparent particle size is almost the same, but it is intended. The effect of improving the moisture permeability cannot be obtained. Urea
Instead of aldehyde resin powder or melamine-aldehyde resin powder or mixed powder thereof, polyurethane resin powder, polyacrylic resin powder, polyolefin resin powder, polysiloxane resin powder, etc. having an average particle diameter of several microns to several tens of microns are used. Even if it is used, the desired effect of improving the moisture permeability is not recognized.

The same effect can be obtained by using a urea derivative such as thiourea or ethylene urea in place of urea, or by using a melamine intermediate such as dicyandiamide or guanamine in place of melamine. As the type of resin, the urea-aldehyde resin powder is superior to the melamine-aldehyde resin powder in that it can be used in applications where weather resistance is required. Further, as the aldehyde component of the resin, formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde, acrolein, glyoxal, malonaldehyde, furfural and the like can be applied, but formaldehyde is particularly suitable.

The sheet or film-shaped resin molded product of the present invention is mainly used as a base material for vinyl chloride leather, synthetic leather, non-woven fabric, or the like, or for vinyl chloride leather, synthetic leather, artificial leather, woven fabric, non-woven fabric, etc. It can be used by laminating, pasting or laminating. By using the sheet or film-shaped resin molded product of the present invention, excellent moisture permeability can be obtained in any application. The moisture permeability evaluation method varies depending on the type of the base material, but mainly the method described in JIS Z0208 or JIS
It can be measured by the method described in L1099, and in the case of vinyl chloride leather, synthetic leather, etc. According to the method described in JIS Z0208, the measurement method under the conditions of 40 ° C. and 90% RH, the moisture permeability per 1 m ² surface 24 hours Can be evaluated with.

The resin molded product of the present invention has a natural-like appearance,
For the purpose of imparting a touch and a function, an organic natural product powder can be added in addition to the urea-aldehyde resin powder, the melamine-aldehyde resin powder or a mixed powder thereof. These organic natural product powders further enhance the effect of improving the moisture permeability by the urea-aldehyde resin powder, the melamine-aldehyde resin powder or the mixed powder thereof, and the urea-aldehyde resin powder, the melamine-aldehyde resin powder or the mixed powder thereof. A natural product-like appearance, soft touch similar to natural leather, moisture absorption and desorption, and other peculiar functions of organic natural product powder, which cannot be obtained by adding only the above, can be imparted. In particular, vinyl chloride leather, synthetic leather, artificial leather It is possible to simultaneously realize the various functions possessed by the natural leather required for such applications.

The organic natural product powder to which the present invention can be applied is not particularly limited, but is particularly effective in leather powder, collagen powder, chitin or chitosan powder, keratin powder, and silk powder. Among them, leather powder and collagen powder are particularly preferable. Organic natural product powder used in the present invention,
The content of particles having a particle size of 100 μm or less is 95% by weight.
The above-mentioned particles are more preferable, the content of particles having a particle size of 60 μm or less is 95% by weight or more, and further preferably the content of particles having a particle size of 40 μm or less is 80% by weight or more. When the content of organic natural product powder having a particle size of 100 μm or more is increased, the mixing property with the resin compound is decreased, and the contact resistance with the cylinder, screw, and die of the molding machine is further increased, which causes a change in injection pressure. It is not preferable because not only the moldability is deteriorated but also the machine base is damaged.

In the present invention, the compounding ratio of the urea-aldehyde resin powder, the melamine-aldehyde resin powder or the mixed powder thereof and the organic natural product powder is not particularly limited, and the compounding ratio is added according to the balance of the imparting function. It For example, when the main purpose is the moisture permeability improving effect, it is preferable to add urea-aldehyde resin powder, melamine-aldehyde resin powder, or a mixed powder thereof in an equal amount or more with respect to the organic natural product powder addition amount, and more preferably. Is added twice or more. The moisture permeability decreases as the proportion of the organic natural powder added increases, but on the contrary, the appearance and feel of natural leather are emphasized.

The thermoplastic resin used for mixing or melt molding is generally a polyethylene resin (low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acryl). Acid copolymer, ethylene-maleic anhydride-acrylic acid copolymer), polypropylene resin (isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene copolymer, propylene-ethylene-butene copolymer), polybutene Resin, polyisobutylene resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin, polyurethane resin, polyurethane acrylate resin, polyester resin (aromatic polyester resin, aliphatic polyester resin), Amide resin, polycarbonate resin, unsaturated polyester resins, alkyd resins, vinyl acetate resins, epoxy resins, epoxy acrylate resins, A
BS resin, polystyrene resin, polyacetal resin and the like, and copolymers thereof are used. If necessary, the resin may contain a plasticizer, a stabilizer, a curing agent, a catalyst, a filler, a colorant, a reactive monomer, a solvent, a dispersant, and various other additives to be used as a resin compound. it can. It may be solid or liquid.

The blending ratio of the urea-aldehyde resin powder, the melamine-aldehyde resin powder or the mixed powder thereof to the resin is determined by the use, shape, requirements, etc. of the molded product obtained by molding the resin composition.
In the sheet or film-shaped resin molded product according to the present invention, urea-based resin is added to 100 parts by weight of the thermoplastic resin.
Aldehyde resin powder or melamine-aldehyde resin powder or a mixed powder thereof is preferably mixed or melt-molded in an amount of 0.1 to 60 parts by weight, more preferably 1 to 50 parts by weight, further preferably 5 to 40 parts by weight. Partial addition is desirable. When the blending amount of the urea-aldehyde resin powder, the melamine-aldehyde resin powder, or the mixed powder thereof is less than 0.1 parts by weight with respect to the thermoplastic resin, the moisture permeability effect cannot be sufficiently obtained, and 60% by weight or more is not obtained. In this case, it is not preferable because it cannot be uniformly dispersed in the resin and the physical properties such as strength and abrasion resistance are greatly deteriorated.

The resin composition thus obtained is subjected to usual melt molding, that is, a thermoplastic resin which softens and melts when heated and can be arbitrarily deformed by applying force, and which solidifies when heat is removed. Then, it can be molded into a sheet or film. It is desirable that the kneading and melt molding of the resin composition be performed under a temperature condition of 250 ° C. or lower. If it exceeds 250 ° C, the aggregate structure may be disintegrated or the urea-aldehyde resin or the melamine-aldehyde resin may be decomposed during kneading or melt molding, and the desired effect of improving the moisture permeability of the resin molded product may not be obtained. . Also when adding organic natural product powder,
Considering their thermal stability, it is preferable to carry out kneading and melt molding at a temperature of 250 ° C. or lower, more preferably 220 ° C. or lower.

[0019]

EXAMPLES The present invention will be described below with reference to specific examples. Example 1 The average particle size of primary particles is 0.1 to 0.5 μm, the average particle size of their aggregates is 4 to 5 μm, and 45 μm.
40 parts by weight of a urea-formaldehyde resin powder (Pergopack M3, manufactured by Lonza Japan) containing 99.9% or more of aggregate particles of m or less is mixed with vinyl chloride resin (manufactured by Shin-Etsu Chemical).
TK-1300) 100 parts by weight together with 50 parts of dioctyl phthalate and kneaded, and calendered to 0.5 mm
The resin composition melt-molded into the sheet of was obtained.

The sheet produced by this method has a moisture permeability of 40 ° C. and 90 ° C. according to the method described in JIS Z0208.
The measurement was performed under the condition of% RH, and the moisture permeation amount per 24 hours of 1 m ² surface was obtained. For appearance, see JIS Z874
According to the method described in 1, the silver surface glossiness in the direction of an angle of 75 degrees of the light irradiated to the sheet surface at an incident angle of 75 degrees was measured using a "digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments". Regarding the tactile sensation, the softness when the surface treatment agent layer was patted on the finger pad was evaluated. Table 1 shows the evaluation results.

Example 2 30 parts by weight of urea-formaldehyde resin powder (Pergopack M3, manufactured by Lonza Japan) used in Example 1 and collagen powder having an average particle size of about 8 μm (Triazet C
10 parts by weight (X260-1, manufactured by Showa Denko) were molded by the same resin and method as in Example 1 to obtain a sheet. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

Example 3 30 parts by weight of urea-formaldehyde resin powder (Pergopack M3, manufactured by Lonza Japan) used in Example 1 and the collagen powder used in Example 2 (Triazet CX)
260-1 Showa Denko) 10 parts by weight and LLDPE
(Sholex Linear: MI = 23 g / 10 min, density 0.916 g / cm ³ , Showa Denko) 100 parts by weight 1
The mixture was melt-kneaded with a kneader at 80 ° C., and then a 0.8 mm sheet was formed by compression molding. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

Example 4 5 parts by weight of a melamine-formaldehyde resin powder (Eposter S, manufactured by Nippon Shokubai) having an average particle diameter of primary particles of about 0.3 μm and having an aggregate particle diameter of several μm by association. 10 parts by weight of leather powder (classified buffing powder generated in the manufacturing process of natural leather) was molded by the same resin and method as in Example 1 to obtain a sheet. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

Example 5 30 parts by weight of the urea-formaldehyde resin powder (Pergopack M3, manufactured by Lonza Japan) and 10 parts by weight of chitosan powder (Chitopearl, manufactured by Fuji Spinning Co., Ltd.) used in Example 1 were used in the same resin as in Example 1. , And a sheet was obtained. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

Comparative Example 1 A sheet was obtained by molding with the same resin and method as in Example 1 without adding both the urea-formaldehyde resin powder and the organic natural product powder. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

Comparative Example 2 Example 2 was performed without adding the urea-formaldehyde resin powder.
50 parts by weight of the same collagen powder as used in Example 1 was added and molded by the same resin and method as in Example 1 to obtain a sheet. The sheet produced by this method is the same as that of Example 1.
Evaluation was carried out in the same manner as in, and the evaluation results are shown in Table 1.

Comparative Example 3 50 parts by weight of polyurethane resin powder (Art Pearl C-800 transparent, manufactured by Negami Kogyo Co., Ltd.) having an average particle size of about 5 μm and a maximum particle size of about 40 μm was used in place of the urea-formaldehyde resin powder. Add the same resin as in Example 1,
A sheet was obtained by molding by the method. The sheet prepared by this method was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.

[0028]

[Table 1] Appearance / Feeling: Good with a silver surface glossiness of 10 or less measured by the method described in JIS Z8741 and having a good soft feeling when stroked with the finger pad, good with one of them, and bad with both. Was designated as x.

[0029]

According to the present invention, urea-aldehyde resin powder, melamine-aldehyde resin powder, a mixed powder thereof, or a powder of these and an organic natural product powder are mixed in a thermoplastic resin at a specific ratio and melted. By molding into a sheet or film, it was possible to obtain a resin molded product with improved moisture permeability and appearance and touch.

Claims (5)

[Claims] 1. 80% by weight of particles having a particle size of 2 μm or less
Containing urea-aldehyde resin powder or melamine-
Aldehyde resin powder is associated, and the aggregate has a particle size of 1
A urea-aldehyde resin powder association, a melamine-aldehyde resin powder association, or a mixed association thereof having a content of not more than 00 μm of 95% by weight or more,
A resin molded product, characterized by being kneaded with a thermoplastic resin and melt-molded into a sheet or film. 2. A urea-aldehyde resin powder association, a melamine-aldehyde resin powder association or a mixed association thereof 0.1 with respect to 100 parts by weight of the thermoplastic resin.
2. The resin molded product according to claim 1, wherein about 60 parts by weight is kneaded with a thermoplastic resin and melt-molded into a sheet or a film. 3. An organic natural product powder having a particle size of 100 μm or less and a content of particles of 95% by weight or more, together with a urea-aldehyde resin powder aggregate, a melamine-aldehyde resin powder aggregate, or a mixed aggregate thereof. The resin molded product according to claim 1, wherein the resin molded product is kneaded with a thermoplastic resin and melt-molded into a sheet or a film. 4. The resin molded product according to claim 1, wherein the aldehyde component of the urea-aldehyde resin powder or the melamine-aldehyde resin powder is formaldehyde. 5. The resin molded product according to claim 3, wherein the organic natural product powder is at least one selected from leather powder, collagen powder, chitin or chitosan powder, keratin powder and silk powder.