JPH0441693B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a resin modifier, and more specifically,
The present invention relates to a resin modifier and a resin modification method capable of imparting excellent surface properties to films, coatings, and other resin molded products. (Prior art) Conventionally, the surfaces of resin molded products such as various films and coatings have excellent stain resistance, water resistance, abrasion resistance,
Adhesion resistance is required, and depending on the application, a low coefficient of surface friction is required. In order to meet these demands, a method of adding a lubricant such as silicone oil, wax, or fatty acid to give the resin molded product lubricity, water resistance, etc. has been used. (Problems to be Solved by the Invention) According to the method described above, the objective is achieved to a certain extent, but in such a method, the lubricant added to the molded product is deposited on the surface of the molded product over time. Since the lubricant bleeds out and causes various problems, the amount of lubricant added is limited to a few percent at most, and therefore the desired performance cannot be fully exhibited. As a method to solve the above-mentioned drawbacks, a method has been proposed that uses a resin with a low coefficient of friction as the resin itself, for example, a polyurethane resin having siloxane bonds in the molecule (for example, JP-A-57
−176535, No. 59-94237, No. 59-5421, No.
No. 58-218034, No. 58-222436, No. 59-11535,
(See Publication No. 59-82636, etc.). According to such a method, it is possible to form a molded article with a relatively low coefficient of surface friction, but since this polyurethane resin having siloxane bonds contains siloxane bonds in the main chain of the polymer, it is possible to form a molded article with a relatively low coefficient of surface friction. It is difficult to achieve a sufficient reaction, making it difficult to obtain a resin of constant quality, resulting in high costs, and various problems arise due to unreacted silicon compounds. Furthermore, since the polymer is limited to polyurethane resin, there is a problem in that the scope of its use is significantly limited. The inventor of the present invention has solved the above-mentioned drawbacks of the conventional technology and, as a result of intensive research in order to meet the above-mentioned demands, has modified resin using a specific modifier to form molded products such as films and coatings. When doing so, the drawbacks of the prior art as described above are solved, the resin is not limited to polyurethane resins, various resins can be easily used, and molded products with excellent surface properties can be provided. Completed the invention. (Means for Solving the Problems) That is, the present invention provides a reaction product of a silicone compound having a reactive functional group and an organic polyisocyanate, which contains a modifier having at least one free isocyanate group. , is a resin modification method characterized by reacting with a resin having a group in its side chain that can react with an isocyanate group. To explain the present invention in more detail, the present invention
The resin modifier characterized in 1 is a reaction product of a silicone compound having a reactive organic functional group and an organic polyisocyanate,
It has at least one free isocyanate group in its molecule. Preferred examples of the silicone compound having a reactive organic functional group used to obtain such a modifier include the following compounds. (1) Amino modified silicone oil (m=1~10, n=2~10, R=CH3 or
OCH3) (m=1~10, n=2~10, R=CH3 or
OCH3) (m=0~200) (n=2~10) (Branch point = 2-3, R = lower alkyl group, 1 =
2-200, m=2-200, n=2-200) (n=1-200, R=lower alkyl group) (2) Epoxy-modified silicone oil (n=1~200) (m=1~10, n=2~10) (n=1~200) (Branch point = 2-3, R = lower alkyl group, 1 =
2-200, m=2-200, n=2-200) (n=1~10) (m=1-10, n=2-10) (3) Alcohol-denatured silicone oil (n=1~200) (m=1~10, n=2~10) (n=0~200) (l=1~10, m=10~200, n=1~5) (n=1-200, R=lower alkyl) (4) Mercapto silicone oil (m=1~10, n=2~10) (n=2~10) (Branch point = 2-3, R = lower alkyl group, 1 =
2-200, m=2-200, n=2-200) (n=1-200, R=lower alkyl group) (5) Carboxyl-modified silicone oil (m=1~10, n=2~10) (n=1~200) (Branch point = 2-3, R = lower alkyl group, 1 =
2-200, m=2-200, n=2-200) (n=1 to 200, R=lower alkyl group) The silicone compounds having the above-mentioned reactive organic functional groups are preferred examples of silicone compounds in the present invention, and the present invention is limited to these examples. Rather, the above-mentioned exemplary compounds and other silicone compounds are currently commercially available and readily available on the market;
Any of these can be used in the present invention. The organic polyisocyanate used in the present invention and the second characteristic of the present invention is a compound having at least two isocyanate atoms in an aliphatic or aromatic compound, and has traditionally been used as a synthetic raw material for polyurethane resins. Widely used. Any of these known organic polyisocyanates are useful in the present invention. Particularly preferred organic polyisocyanates are as follows. Toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1, 3-phenylene diisocyanate, 2,4-diisocyanate-diphenyl ether, mesitylene diisocyanate, 4,4-methylenebis(phenyl isocyanate), diylylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate , 4,4-dibenzyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, and adducts of these organic polyisocyanates with other compounds, such as those having the following structural formula, but are not limited thereto. (however,

[Formula]) The resin modifier of the present invention combines a silicone compound having a reactive organic functional group as described above and an organic polyisocyanate as described above, such that the reactive organic functional group and the isocyanate group are present in one molecule. in the presence or absence of an organic solvent and a catalyst, at a functional group ratio of one or more, preferably 1 to 2, isocyanate groups in excess of about 0 to 150°C, preferably
It can be easily obtained by reacting at a temperature of 20 to 80°C for about 10 minutes to 3 hours. The organic solvent that may be used in the production of such a modifier may be any organic solvent as long as it is inert to each reaction raw material and product. For example, preferred organic solvents include methyl ethyl ketone, methyl -n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate,
Ethyl acetate, butyl acetate, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, methyl cellosolve, butyl cellosolve, cellosolve acetate, dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane, heptane, octane, mineral spirits , petroleum ether, gasoline, benzene, toluene, xylene, chloroform, carbon tetrachloride, chlorobenzene, perchlorethylene,
Examples include trichlorethylene. When the resin modifier of the present invention obtained as described above is produced using an organic solvent, it can be separated from the organic solvent or can be used as a solution of the organic solvent. The modifier of the present invention separated from the organic solvent is generally in the form of a white to brown liquid or solid, and is easily soluble in various organic solvents. According to various analyzes such as infrared absorption spectrum, elemental analysis, and molecular weight measurement, the modifier of the present invention as described above shows that the isocyanate group of the organic polyisocyanate and the reactive organic functional group of the silicone compound undergo an addition reaction. For example, when the reactive organic functional group is an amino group, it is clear that the two are bonded through an -NHCONH- bond and that the compound has at least one free isocyanate group in one molecule. It became. According to the inventor's detailed research, the modifier of the present invention has free isocyanate, so
For example, it is reactive with various resins having hydroxyl groups, primary and secondary amino groups, amide groups, carboxyl groups, etc., and is not bonded to the main chain of these resins but as a side chain. Therefore, it was discovered that when molded products are formed from resin, various surface properties such as significantly lowering the coefficient of friction of the molded products can be improved without degrading the various properties inherent in the resin. . Moreover, such an unexpected effect is due to the fact that the modifier of the present invention has free isocyanate groups, so that the isocyanate groups are converted into isocyanate groups before, during, or after forming a molded article, for example, a coating. This is because it also acts as a type of modifier that reacts with each other or with the resin. In the present invention, the resin modified with the resin modifier described above has groups capable of reacting with isocyanate groups such as hydroxyl groups, primary to secondary amino groups, amide groups, carboxyl groups, and urethane bonding groups as side chains. For example, vinyl chloride resins with these reactive groups introduced, vinylidene chloride resins, vinyl chloride/vinyl acetate/vinyl alcohol copolymer resins, alkyd resins, epoxy resins, acrylonitrile-butadiene. Examples thereof include polyurethane resins, polyurea resins, nitrocellulose resins, polybutyral resins, polyester resins, silicone resins, melamine resins, urea resins, acrylic resins, and polyamide resins. These resins can be used alone or as a mixture, and can be used as a solution or dispersion in an organic solvent. Further, the reaction between the resin and the modifier can be carried out in the presence or absence of an organic solvent and a catalyst.
At a temperature of 150℃, preferably 20-80℃ for about 10 minutes ~
This can be easily carried out by reacting for 3 hours. To form a molded article, for example, a film, it is preferable to dissolve or disperse the resin modified with the above-mentioned modifier in the above-mentioned medium and use it in the form of a paint. Of course, the form of use is not limited to paint type. For example, in paint form, the concentration of the resin may range from about 1 to
Approximately 50% by weight is preferred, and the modifier can be used in a proportion of about 1 to 100 parts by weight per 100 parts by weight of these resins. The reaction between the modifier and the resin may be carried out at any time, such as during or after the formation of the composition for forming a molded article, during or after the formation of the molded article. In addition, if the resin does not have a group that reacts with isocyanate groups, the modifiers may react with each other, or if water or a polyfunctional compound such as a polyamine is added, the modifier will have a high molecular weight and react with the reactive resin. It has the same effect as when used. (Action/Effect) The resin modifier of the present invention as described above is not limited to a specific resin, but is useful for modifying various resins,
Depending on the type of modified resin, the resin can be formed from the modified resin while retaining its various properties such as strength, flexibility, electrical, chemical, and physical properties. surface properties of the molded product,
For example, stain resistance, water resistance, abrasion resistance, adhesion resistance, heat resistance, etc. can be significantly improved, and the friction coefficient of molded products can be significantly reduced. Furthermore, the modifier of the present invention does not become the main chain of the resin, but rather binds to the main chain of the resin and becomes a side chain of the resin, unlike conventional polyurethane resins containing siloxane bonds. , without deteriorating the excellent performance originally possessed by the resin. In addition, the modifier of the present invention reacts with each other or with the resin in the molded product, has a high molecular weight, and is integrated with the resin. This solves the drawback that additives bleed onto the surface of molded products, causing various problems. Therefore, it is possible to incorporate a large amount of modifier into molded products, and as a result, the surface properties of molded products are improved. can be improved. Next, the present invention will be explained in more detail by giving Examples, Usage Examples, and Comparative Examples. In the text, parts and percentages are based on weight. Example 1 (Production example of modifier) 175 parts of an adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, manufactured by Nippon Polyurethane, NCO% 12.5, solid content 75%) was heated at 50°C. While stirring well,
88 parts of terminal aminopropyl polydimethylsiloxane (molecular weight 2200) having the structure shown below is gradually added dropwise to the mixture and reacted. (n is a value giving a molecular weight of 2200) After the reaction was completed, 976 parts of a transparent liquid modifier (M1) was obtained which evaporated ethyl acetate. According to the infrared absorption spectrum of this modifier,
Absorption due to free isocyanate groups at 2270/cm remained, and an absorption band due to Si-O-C groups was shown at 1090/cm. Also, when quantifying the free isocyanate group in this modifier, the theoretical value is 0.83.
%, whereas the actual value was 0.78%. Therefore, the main structure of the above modifier is estimated to be the following formula. Example 2 (Production example of modifier) Add 24 parts of phenyl isocyanate to 196 parts of terminal hydroxypropyl polydimethylsiloxane (molecular weight 980) having the following structure, stir well at 60°C, and react to produce a transparent liquid reaction product. (A) 213 copies were obtained. (n is the value at which the molecular weight is 980) Next, an adduct of hexamethylene diisocyanate and water (Dyuranate 24A-100, manufactured by Asahi Kasei,
NCO%23.5) 52 parts at 60℃ while stirring well.
220 parts of the above reaction product (A) was gradually added dropwise to this mixture to react, and a colorless and transparent liquid modifier (M2) was obtained.
part was obtained. According to the infrared absorption spectrum of this modifier,
Absorption due to free isocyanate groups at 2270/cm remained, and an absorption band due to Si-O-C groups was shown at 1090/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 1.54%, while the actual value was 1.37%. Therefore, the main structure of the above modifier is estimated to be the following formula. Example 3 (Production example of modifier) To 230 parts of terminal aminopropyl polydimethylsiloxane (molecular weight 1150) having the following structure, n-
Add 15 parts of butyraldehyde and stir well to react at 80°C. React for 3 hours while removing the generated water from the system under reduced pressure to obtain 238 parts of a transparent liquid reaction product (B). . (n is the value at which the molecular weight is 1150) Next, an adduct of 1 mol of trimethylolpropane and 3 mol of xylene diisocyanate (Takenate D110N, manufactured by Takeda Pharmaceutical, NCO% 11.5, solid content
While stirring well at room temperature, 490 parts of the above reaction product (B) was gradually added dropwise to 186 parts of 75%).
The reaction was carried out at ℃. After the reaction was completed, ethyl acetate was evaporated to obtain 610 parts of a transparent liquid modifier (M3). According to the infrared absorption spectrum of this modifier,
Absorption due to free isocyanate groups at 2270/cm remained, and an absorption band due to Si-O-C groups was shown at 1090/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 1.34%, while the actual value was 1.25%. Therefore, the main structure of the above modifier is estimated to be the following formula. Example 4 (Production example of modifier) While stirring 35 parts of 2,6-tolylene diisocyanate and 110 parts of ethyl acetate at 60°C, a terminal mercaptopropyl polydimethylsiloxane (molecular weight 1580) having the following structure was added. Gradually add 316 parts to react. (L, m, and n are values that give a molecular weight of 1580.) After the reaction was completed, ethyl acetate was evaporated to obtain 340 parts of a transparent liquid modifier (M4). According to the infrared absorption spectrum of this modifier,
Absorption due to free isocyanate groups at 2270/cm remained, and an absorption band due to Si-O-C groups was shown at 1090/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 2.39%, while the actual value was 2.12%. Therefore, the main structure of the above modifier is estimated to be the following formula. (l, m, n are the values that make the molecular weight 1580) Example 5 (Production example of modifier) 52 parts of hexamethylene diisocyanate and 160 parts of ethyl acetate were stirred well at 60°C, and 450 parts of terminal hydroxypropyl polydimethylsiloxane (molecular weight 2250) having the following structure was added thereto. Gradually drop it and let it react. (n is the value at which the molecular weight is 1580) After the reaction was completed, ethyl acetate was evaporated to obtain 488 parts of the modifier (M5) in the form of a transparent liquid. According to the infrared absorption spectrum of this modifier,
Absorption due to free isocyanate groups at 2270/cm remained, and an absorption band due to Si-O-C groups was shown at 1090/cm. Furthermore, when the amount of free isocyanate groups in this modifier was quantified, the theoretical value was 1.67%, while the actual value was 1.52%. Therefore, the main structure of the above-mentioned modifier is estimated to be the following formula. Example 6 (Modification of resin) 150 parts of polybutylene adipate having a molecular weight of 2,000 having a hydroxyl group at the end, 20 parts of 1,3-butylene glycol, and 52 parts of tolylene diisocyanate were subjected to an addition reaction in 412 parts of methyl ethyl ketone to obtain a viscosity of 200 poise/ Polyurethane resin solution at 20℃ (solid content 35
%) was obtained. To 100 parts of this polyurethane resin solution,
5 parts of the modifier (M1) were added and reacted at 80°C for 3 hours to obtain a modified resin solution (UR1) in which the modifier and the polyurethane resin were combined. In the resin obtained above, no isocyanate group was observed by infrared absorption spectrum. This is presumed to be because the modifier was grafted onto the resin. Example 7 (Modification of resin) A modified resin solution (UR2) was obtained in the same manner as in Example 6 except that a modifier (M2) was used in place of the modifier (M1) in Example 6. Example 8 (Modification of resin) A modified resin solution (UR3) was obtained in the same manner as in Example 6 except that a modifier (M3) was used in place of the modifier (M1) in Example 6. Example 9 (Modification of resin) A modified resin solution (UR4) was obtained in the same manner as in Example 6 except that a modifier (M4) was used in place of the modifier (M1) in Example 6. Example 10 (Modification of resin) A modified resin solution (UR5) was obtained in the same manner as in Example 6 except that a modifier (M5) was used in place of the modifier (M1) in Example 6. Application example 1 Using the five types of resin solutions obtained above, a transparent film was formed by coating and drying on a glass plate to a dry film thickness of 10 μm, and its static friction coefficient and surface When the condition was determined, the results shown in Table 1 below were obtained. In addition, Comparative Example 1 uses a resin solution before modification, and Comparative Example 2 uses silicone oil (SH) in the resin solution before modification.
-200, manufactured by Toray Silicone).

[Table] The static friction coefficient is the value measured using a sliding tester (manufactured by Toyo Seiki), and the surface condition is the state when the film was left for 5 days after film formation. ○ indicates no change, × indicates silicone Indicates that a large amount of oil has bleed out from the surface. As described above, according to the present invention, it is possible to significantly reduce the static friction coefficient of a molded product and maintain a good surface condition. Example 11 (Modification of resin) While stirring 200 parts of acrylic polyol (Hytaloid 3001, manufactured by Hitachi Chemical, solid content 50%),
Add 5 parts of Modifier M1 and 5 parts of butyl acetate,
A modified resin solution (AR1) in which the modifying agent and resin were combined by a time reaction was obtained. In the modified resin obtained above, no isocyanate group was observed by infrared absorption spectrum. This is presumed to be due to graft bonding of the modifier to the resin. Example 12 (Modification of resin) A modified resin solution (AR2) was obtained in the same manner as in Example 11 except that a modifier (M2) was used in place of the modifier (M1) in Example 11. Example 13 (Modification of resin) A modified resin solution (AR3) was obtained in the same manner as in Example 11 except that a modifier (M3) was used in place of the modifier (M1) in Example 11. Example 14 (Modification of resin) A modified resin solution (AR4) was obtained in the same manner as in Example 11 except that a modifier (M4) was used in place of the modifier (M1) in Example 11. Example 15 (Modification of resin) A modified resin solution (AR5) was obtained in the same manner as in Example 11 except that a modifier (M5) was used in place of the modifier (M1) in Example 11. Application example 2 Using each of the above modified resins AR1 to AR5, the following formulations were kneaded using three rolls to prepare five types of paints, and the film thickness when dry was 40~40 mm on a zinc phosphate treated steel plate.
A coating film was formed by coating and drying to a thickness of 45 μm. Modified resin 63 parts Titanium white 35 parts Takenate Q-110N 6.5 parts Toluene 45 parts Methyl ethyl ketone 30 parts Cellosolve acetate 25 parts The stain resistance and surface condition of the coating film obtained above were as shown in Table 2 below. Comparative Example 1 is a case where a resin solution before modification is used, and Comparative Example 2 is a case where 5 parts of silicone oil (SH-200, manufactured by Toray Silicone) is added to a resin solution before modification.

[Table] The stain resistance is for lipstick (A) and oil-based felt-tip pen.
After writing letters on the coating film in (B) and leaving it at 30℃ for 24 hours,
These are the results of wiping with a cloth, where ◯ indicates that no contamination remains, and △ indicates that slight contamination remains. Abrasion resistance (mg) is the ASTM abrasion resistance test,
Using CS10 as a wheel, applying a load of 500g, 1000
This is a value measured by rotation, and the surface condition is 5 minutes after film formation.
This is the state after being left for days, where ◯ indicates no change and × indicates that a large amount of silicone oil has bled out from the surface. As described above, according to the present invention, the stain resistance and abrasion resistance of molded products are significantly improved, and a good surface condition can be maintained. Usage example 3 The resin solutions UR1 to UR5 obtained in the examples were
Each coated with a reverse roll coater to a thickness of 15 μm.
A heat-resistant layer was formed by coating each film on a polyester film with a dry thickness of 1 μm, and drying the solvent. Next, a magnetic layer is formed on the opposite surface using a conventional method from a dispersion containing Co-containing γ-Re ₂ O ₃ and a binder resin consisting of a normal polyurethane resin and a vinyl chloride copolymer resin, and a magnetic layer is formed to a predetermined width. Five types of magnetic recording media were obtained. The performance of these magnetic recording media was as shown in Table 3 below. Note that Comparative Example 1 is a case where a resin solution before modification was used.

[Table] The coefficient of friction (A) is the value (μk) measured between the magnetic layer and the molded article. Observations include squealing (B), lateral wobbling of jitter (C), irregular winding of the tape during fast forwarding (D), and wear of the magnetic layer (E). The overall evaluation was given as F. From the above results, it is clear that the magnetic recording medium using the modifier of the present invention has a low friction coefficient of the heat-resistant layer and exhibits excellent running characteristics. Example 16 (Modification of resin) To 100 parts of a methyl ethyl ketone solution (solid content 30%) of vinyl chloride/vinyl acetate/vinyl alcohol copolymer resin (Eslec A, manufactured by Sekisui Chemical Co., Ltd.),
Add 3 parts of the modifier (M1) obtained in Example 1 and heat at 80°C.
The mixture was reacted for 3 hours to obtain a modified resin solution (VR1) in which the modifying agent and the vinyl resin were combined. In the resin obtained above, no isocyanate groups were observed by infrared absorption spectrum. This is presumed to be due to graft bonding of the modifier to the resin. Example 17 (Modification of resin) A modified resin solution (VR2) was obtained in the same manner as in Example 16 except that a modifier (M2) was used in place of the modifier (M1) in Example 16. Example 18 (Modification of resin) A modified resin solution (VR3) was obtained in the same manner as in Example 16 except that a modifier (M3) was used in place of the modifier (M1) in Example 16. Example 19 (Modification of resin) A modified resin solution (VR4) was obtained in the same manner as in Example 16 except that the modifier (M4) was used in place of the modifier (M1) in Example 16. Example 20 (Modification of resin) A modified resin solution (VR5) was obtained in the same manner as in Example 16 except that a modifier (M5) was used in place of the modifier (M1) in Example 16. Usage example 4 Co-containing Fe ₂ O ₃ 100 parts Any one of the above resin solutions VR1 to VR5 (30%
solution) 20 parts polyester-type polyurethane resin solution (Rezamin
ME12, manufactured by Dainichiseika Chemical Industries) 54 parts Dispersant (lecithin) 1 part Carbon black 5 parts Nitrocellulose 6 parts Methyl ethyl ketone 270 parts The above ingredients were mixed and kneaded in a ball mill for 50 hours, then 8 parts of Coronate L was added and an additional 3 hours After kneading, the kneaded mixture was passed through a filter to obtain a dispersion of five types of magnetic particles. The five types of dispersions obtained above were applied to a polyester film with a thickness of 15 μm each using a reverse roll coater to a thickness of 5 μm, and after drying the solvent, the surface was coated with a super calendar roll. The magnetic recording media were processed and cut into predetermined widths to obtain magnetic recording media. When the performance of the above magnetic recording medium was investigated, the results shown in Table 4 below were obtained.
Note that Comparative Example 1 is a case where a resin solution before modification was used.

【table】

[Table] The coefficient of friction (A) is the value (μk) measured between the magnetic layer and the support (base film).
Observations are made of tape squeal (B), jitter lateral wobbling (C), irregular winding during fast forwarding of the tape (D), and wear of the magnetic layer (E) during 200 runs. The overall evaluation was given as F. From the above results, it is clear that the magnetic recording medium using the modifier of the present invention has a low coefficient of friction in the magnetic layer and exhibits excellent running characteristics.

Claims (1)

[Claims] 1 A reaction product of a silicone compound having a reactive functional group and an organic polyisocyanate,
A method for modifying a resin, which comprises reacting a modifier having at least one free isocyanate group with a resin having a group in its side chain that can react with the isocyanate group.