JP2725835B2 - Synthetic resin modifier, modified resin material, modified resin film, and modified surface treatment products - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a synthetic resin modifier, a modified resin material, a modified resin film, and a modified surface-treated product. Modifiers and surface treatments added to modified resin materials for surface treatments to improve various properties such as texture and hygroscopicity, such as texture and gloss, for various products consisting of Modified resin material that is used as a raw material for paints and film production, modified resin film that is laminated on the product surface to modify its surface, or used as a product by itself, It relates to a product that has been subjected to a surface treatment for improvement.

[Conventional technology]

Synthetic resin products and the like have different surface gloss and texture depending on the properties of the material itself, and have various feelings.However, in order to give the user a favorable feel and aesthetic appearance, it is not preferable to use the material as it is, Often it is necessary to improve the feel. On the other hand, properties on the surface of various products, for example, hygroscopicity, may greatly affect not only the use performance of the products but also the feeling.

For example, synthetic leather and synthetic fibers have a considerably different feel and surface properties from natural materials, and in order to make this feel closer to natural materials, it is necessary to apply a modifying coating agent or paint. For example, a film that has been subjected to a modification treatment such as a feeling improvement is laminated on the surface.

As a specific example of a conventional surface modifying material such as a synthetic resin product, there is a polyurethane resin used for surface treatment of nylon or polyester fabric for the purpose of improving moisture permeability. However, the polyurethane has good moisture permeability improving effect and the like, but has a sticky feeling on the surface, and the surface gloss is too strong.
There was a problem that the texture of the fabric was impaired.

Therefore, in order to improve the feeling of the polyurethane, it has been proposed to add a fine powder (particle size: about 5 μm) of gelatin and collagen fibers (coarse collagen or cowhide powder) to the polyurethane. It is disclosed in, for example, Japanese Patent Publication No. 99300. By the addition of such a fine powder, polyurethane is preferable for surface processing of the nylon cloth or the like as a surface processing agent having good moisture absorption / desorption properties, a dry touch feeling, dew condensation suppression, high water vapor permeability, and the like. Have been.

[Problems to be solved by the invention]

However, in order to add the fine powder to the polyurethane resin, the powder is mixed with the resin material in a dry powder state. In addition, there have been problems that irregularities such as feeling tend to occur easily and moldability when molding a resin material is deteriorated.

In order to mix the powdered gelatin into the resin evenly,
Heat mixing at a high temperature is considered.For example, it has been proposed to heat-knead gelatin at the stage of thermoforming the resin.However, in order to uniformly mix powdered gelatin with the resin, at least about 70 ° C. It is necessary to heat to such a high temperature, and if gelatin is heated to such a high temperature, the gelatin will be degraded or decomposed, and the desired effect of modifying the resin material will not be achieved.

In order to improve the stability (no sedimentation or separation, etc.) when powdered gelatin is added to a synthetic resin, or to improve the performance (surface roughness, etc.) of a resin molded product, gelatin must be added. It is necessary to control the particle size to be small and strictly controlled. For example, it has been conventionally proposed to use gelatin powder having a particle size of 10 μm or less. There is a disadvantage that complicated processing and production conditions are required, such as formation or the water content of gelatin is kept to 5% or less, and the cost is high. Furthermore, it was considered that gelatin was mixed with the resin in a state of being swollen in water, but uniform mixing was difficult as in the case of powder.

Therefore, if gelatin or collagen is mixed with the polyurethane resin in the state of an aqueous solution, the mixture can be uniformly mixed with the resin and the above problem can be solved. When added, another problem arises in that the resin is blocked and cannot be used for the modified surface treatment.

In particular, the above-mentioned method of molding a polyurethane resin includes a method of performing heat molding in the same manner as a normal thermoplastic resin and the like, and dissolving the resin in an organic solvent to form a film, and then evaporating and evaporating the organic solvent. There is a method of fixing the resin film. Among them, in the heat molding method, since the polyurethane resin is heated to a high heat, the polyurethane resin contains the gelatin aqueous solution, when it is in a so-called water-containing state, the polyurethane resin undergoes hydrolysis, thickening, solidification or separation occurs, The polyurethane resin cannot be used for the modified surface treatment or the like. Therefore, it is only necessary to adopt a solution molding method using an organic solvent that does not need to be heated to high heat.However, when an organic solvent is added together with gelatin, a normal gelatin aqueous solution is used.
Due to poor compatibility with the container solvent, it cannot be added to the resin at the same time as the organic solvent. Even if an attempt is made to adjust the viscosity of the resin by adjusting the amount of the organic solvent to be added, there is a problem that the viscosity of the resin cannot be adjusted by the organic solvent because the gelatin itself is thickened or solidified by the addition of the organic solvent. .

Modification of synthetic resin by adding gelatin or collagen can be applied not only to polyurethane resin for surface processing such as nylon cloth as described above, but also to modification of various synthetic resins used for various applications. Again, a similar problem occurred.

Accordingly, an object of the present invention is to provide a modifier which is formed of the above aqueous solution and which can be added to a synthetic resin material which dislikes water, and which has good performance by using this modifier. An object of the present invention is to provide a modified resin material, a modified resin film, and a product subjected to a modified surface treatment.

[Means for solving the problem]

In order to solve the above-mentioned problems, among the present invention, the modifier according to claim 1 has an aqueous solution of the polypeptide lower than the isoelectric point.
Adjust to pH.

According to a second aspect of the present invention, in the first aspect, the aqueous solution of the polypeptide comprises a salt.

The modified resin material according to claim 3 is such that the modifier according to claim 1 or 2 is added to the resin material together with the organic solvent.

A modified resin film according to a fourth aspect is manufactured from the modified resin material according to the third aspect.

The modified surface-treated product according to the fifth aspect is surface-treated with the modified material according to the third aspect.

Polypeptide is a compound having a so-called peptide chain, such as a water-soluble component obtained by decomposing a gelatin raw material such as collagen into water.In addition to collagen, soybean,
Those composed of plant proteins such as wheat and those composed of animal proteins such as casein and plasma can be used. The method for producing the polypeptide varies depending on the raw material, and is not limited. For example, a method obtained by preliminarily treating a gelatin raw material with an alkali and extracting the raw material with water is preferable. Although the isoelectric point (IEP) of the aqueous polypeptide solution varies depending on the production method, the contained components, and the like, the isoelectric point (IEP) of the aqueous alkali-pretreated polypeptide solution is pH 4.7.

To adjust the pH value of the aqueous polypeptide solution, an organic acid such as citric acid or a mineral acid is added. The pH value may be lower than the isoelectric point, but is preferably 0.5 or more lower than the isoelectric point.
It is to be carried out with the H value.

It is preferable to add salts such as sodium chloride (NaCl) to the aqueous polypeptide solution. The pH adjustment is performed with the above salts added. The amount of salts added is preferably 1.0 to 2 with NaCl based on 30.0 parts by weight of the polypeptide.
It is carried out at 0.0 parts by weight, more preferably 5.0 to 15.0 parts by weight.

A modifier consisting of an aqueous polypeptide solution with an adjusted pH value is added to an appropriate synthetic resin material to produce a modified resin material, and a product that undergoes surface modification, such as a paint or film, from this modified resin material Is prepared in a state that can be processed.

As the synthetic resin constituting the modified resin material, a polyurethane resin is preferable, but a resin made of another synthetic resin can also be used, and it is particularly preferable to apply to a synthetic resin which dislikes water. In order to add a modifier to a modified resin material, by adding an organic solvent to the modifier in advance and dissolving it in the resin material and mixing the resin material, blocking solidification of the resin material and the like can be prevented, The mixing of the modifier and the resin material can be performed uniformly. The amount of modifier added to the resin material is
For example, in the case of a urethane resin, it is preferable to add a modifier so that the polypeptide solid content is 1.0 to 40.0% by weight relative to the resin solid content, and more preferably 5.0 to 30.0% by weight. . However, depending on the components of the resin material and the modifier, it can be carried out even outside the above-mentioned range.

As an organic solvent, N, N-dimethylformamide (DM
There are hydrophilic solvents such as F) and methyl ethyl ketone (MEK), and non-hydrophilic solvents such as ethyl acetate and toluene. Either solvent can be used, but hydrophilic solvents capable of dissolving a modifier containing water well can be used. Nonionic solvents are preferred. The organic solvent as described above can be used alone, but by using a plurality of organic solvents in combination, the solubility of the modifier and the stability of the synthetic resin can be improved. The specific type and amount of the organic solvent can be appropriately selected depending on the type of the synthetic resin and the properties of the modifier.

The modified resin material may contain an appropriate additive as needed in addition to the modifier. For example, when using a modified resin material as a paint, such as pigments and solvents,
Components contained in ordinary paints are blended.

The modified resin film is produced from the modified resin material by an ordinary film production method. Also in this case, various components necessary for film production are blended in the modified resin material.

The modified resin film can be used for desired applications as it is, but the surface of the product is modified by bonding the modified resin film to the surface of a product made of various synthetic resins or fibers. be able to. The same surface treatment can be performed by applying a paint produced from the modified resin material on the surface of the product.

The product to be subjected to the modified surface treatment can be applied to a product made of synthetic resin, metal, wood or any other material, and the shape and structure of the product are not limited. Specifically, for example, it can be applied to the surface treatment of the front and back surfaces of a fabric made of synthetic fibers such as nylon and polyester, and natural fibers such as cotton, wool, and silk, and the surface of a synthetic resin film made of foamed polyurethane and the like can be modified. The surface-treated product can be adhered to a fiber fabric to produce a product whose modified surface has a leather-like feel or properties. Specific surface treatment method, depending on the shape, material or application of the product, an appropriate method is selected from various normal surface treatment methods, as the modified resin material used in the surface treatment method, Such a configuration may be used.

[Action]

The modifier obtained by adjusting the aqueous polypeptide solution to a pH value lower than the isoelectric point has good compatibility with an organic solvent.

If a water-containing modifier is added directly to a resin material that dislikes water, the resin will block and solidify, making it unusable as a modified resin material. When is added to the resin material, the resin becomes stable and the modifier can be mixed uniformly and satisfactorily. When salts are contained in the aqueous polypeptide solution, the compatibility between the modifier and the organic solvent is further increased. If a paint or a film is produced from a modified resin material in which a modifier is well mixed, the surface modification of various products can be satisfactorily performed, and the feel and properties of the surface are improved satisfactorily. Products can be obtained.

〔Example〕

-Production of modifier-Alkali-treated gelatin was used as the gelatin constituting the polypeptide. The isoelectric point of this gelatin was pH 4.7. The aqueous solution containing the polypeptide was dissolved by heating at 50 to 55 ° C., sodium chloride was added, and the pH value was adjusted with citric acid. A plurality of types having different amounts of sodium chloride added and adjusted pH values were produced as shown in Table 1 below.

-Compatibility of the modifier with the organic solvent- To 20 parts by weight of the samples A to D, the DMF was added as a hydrophilic organic solvent, and the limit of the solution at which the turbidity, insolubilization, gelation, etc. did not occur. The amount of DMF added was measured, and the results are shown in Table 2.

In Table 2, DMF% was calculated from the DMF addition amount Dw (parts by weight) according to the following equation.

DMF% = Dw ÷ (Dw + 20) × 100 From the results in Tables 1 and 2, Examples A and B (pH value = 4) in which the pH value of the modifier is smaller than the isoelectric point (4.7 in this case) .
No. 0) proved to be able to be mixed well with a much larger amount of organic solvent as compared with Comparative Examples C and D (pH value = 5.0) having a large pH value, that is, to have high compatibility. Comparing Examples A and B also shows that adding a salt to the modifier further increases the compatibility.

-Modified resin material-The following preparation liquid was prepared in order to manufacture a modified resin material using the above modifier.

(1) Polyester urethane resin agent 50 parts by weight (Resamine ME-88NFLP: manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 30%) (2) Modifier (A agent of the above example) 10 parts by weight (water 6 parts by weight) (3) Organic solvent 20 parts by weight As for the organic solvent, N, N-dimethylformamide (DMF) and methyl ethyl ketone (ME
K) was used in the ratio shown in Table 3 below.
Table 3 shows the properties of the prepared preparations.

From the results in Table 3, when only the modifier is added to the resin material as in Comparative Example 4, blocking solidification of the resin occurs, and a good modified resin material cannot be produced.
By adding an organic solvent as in Examples 1 and 2,
It has been demonstrated that the modifier can be homogeneously mixed with the resin material. When the organic solvent is DMF or MEK alone as in Comparative Example 1 or Comparative Example 3, solidification of the resin or coagulation of the protein occurs, so that a good modified resin material cannot be produced, and DMF and MEK cannot be produced. When combining MEK, it is necessary to mix both at an appropriate ratio.

-Modified resin film-Modified resin material consisting of the above-prepared liquid, stretched appropriately on the surface of the support to form a thin film, to produce a polyurethane film by evaporating the solvent at 130 ~ 150 ℃, The results of the responsive evaluation of the performance are shown in the fourth section below.
It is shown in the table. The components of the mixture were as shown in Table 4.

From the results in Table 4, it can be seen that the polyurethane film made of the modified resin material to which the modifier according to the present invention is added has improved surface feel and gloss as compared with those without the modifier added, and the so-called dry touch. It was proved that a matte film with a feeling was obtained.

〔The invention's effect〕

As described above, of the present invention, the modifier according to the first aspect of the present invention comprises an aqueous solution of a polypeptide, and the pH value thereof is adjusted to be lower than the isoelectric point.
An excellent modifier that can be uniformly and well mixed when added to a resin material, is easy to manufacture and handle, and can improve the texture and properties of the surface of resin products. Can be provided.

The modifier according to the second aspect of the present invention has, in addition to the effects described in the first aspect, a phase when the modifier is dissolved in an organic solvent by adding salts to an aqueous solution of the polypeptide. The solubility is improved, and when added to the resin material together with the organic solvent, the mixture is more uniformly and well mixed.

The modified resin material according to the third aspect of the invention is a high-quality modified resin in which the modifier is uniformly mixed by using the modifier according to the first or second aspect of the invention together with an organic solvent. Materials can be provided.

In the modified resin film according to the fourth aspect of the present invention, by using the modified resin material according to the third aspect of the present invention, the modifying agent is uniformly mixed, and the feeling and properties of the surface are uniform and good. It is possible to provide a modified resin film.

The modified surface-treated product according to the fifth aspect of the present invention is provided with a surface treatment using the modified resin material according to the third aspect of the present invention, so that the texture and properties of the surface are uniformly and favorably improved. Product can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location D06M 15/15 D06M 15/15 D06N 3/14 102 D06N 3/14 102

Claims (5)

(57) [Claims] 1. The method of claim 1, wherein the aqueous solution of the polypeptide is lower than the isoelectric point.
Synthetic resin modifier adjusted to pH. 2. The synthetic resin modifier according to claim 1, wherein the aqueous solution of the polypeptide contains salts. 3. A modified resin material obtained by adding the modifier according to claim 1 together with an organic solvent. 4. A modified resin film produced from the modified resin material according to claim 3. 5. A modified surface-treated product which is surface-treated with the modified resin material according to claim 3.