JPS63213535A - Resin modifier and modification of resin - Google Patents

Abstract

PURPOSE:To obtain a modifier providing the surface of various films, coating films or molded articles with excellent stain resistance and wear resistance, comprising a reaction product of a reactive organic functional group-containing fluorine compound and an organic polyisocyanate. CONSTITUTION:A modifier which is a reaction product of a reactive organic functional group-containing fluorine compound and an organic polyisocyanate and substantially contains no liberated isocyanate group. The modifier is added to resins and used. H(CF2CF2)nCH2OH (n=1-7), CF3(CF2CF2)nCH2CH2OH (n=1-10), etc., are preferable as the fluorine compound. Toluene-2,4- diisocyanate, etc., are used as the organic polyisocyanate. The functional group ratio of the reactive organic functional group and the isocyanate group is preferably 1:1 not to leave isocyanate group in the reaction.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin modifier, and more particularly, to a resin modifier that can impart excellent surface properties to films, coatings, and other resin molded products. This invention relates to a method for modifying resin.

(Prior art) Conventionally, the surfaces of resin molded products such as various films and coatings have been required to have excellent stain resistance, water resistance, abrasion resistance, and adhesion resistance, and depending on the application, low surface friction has been required. A coefficient is required.

In order to meet these demands, a method has been used in which a lubricant such as silicone oil, wax, or fatty acid is added to the resin molded product to impart lubricity, water resistance, etc.

(Problem 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. Because it 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 in which a resin with a low coefficient of friction is used as the resin itself, for example, a polyurethane resin having a siloxane bond in the molecule (for example, Japanese Patent Laid-Open No. 57-176535 , same 59
-94237, 59-5421, 58-218
No. 034, No. 58-222436, No. 59-1153
No. 5, 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 carry out a sufficient reaction, it is difficult to obtain a resin of constant quality, the price is high, and various problems arise due to unreacted silicone compounds. Furthermore, since the polymer is limited to polyurethane resins, there is a problem in that the range of use thereof is significantly limited.

The inventor of the present invention solved the drawbacks of the prior art as described above and as a result of intensive research in order to meet the above demands, the inventor modified the 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 between a fluorine compound having a reactive organic functional group and an organic polyisocyanate, which is substantially free of free isocyanate groups. Adding to a resin a resin modifier characterized by: a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate, the modifier having substantially no free isocyanate groups; This is a resin modification method characterized by the following.

To explain the present invention in more detail, the resin modifier of the present invention is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate, and the reaction product substantially eliminates free isocyanate groups. It does not have a specific purpose.

The fluorine compound having a reactive organic functional group used to obtain such a modifier may be any compound having a group capable of reacting with an isocyanate group such as an amino group, a carboxyl group, a hydroxyl group, a thioalcohol group, etc. A particularly preferred example is a fluorine compound represented by the following formula. (1) H(CF2CF2), CH,
OH (n-1 to 7) (2) CFs ((:F2CF
2) nco2Ct12o)1 (n-1 to 10)
(3) CF3((:F2CF2) nC00)l
(n=1 to 10) (4) CFi(CF2CF2)n
C1hC)I2SH(n-1 to 10)(5) H(C
FzCF2)+(CHa)-(OCHzGHz(OH)
11; I2) nOH (1-1 to 10.mal to 1O
1n-1 to 3) (6) F(CFzCF2)+(OL
)-(OCHzClb(Oll)C112). 0■(1
-1 to 1G, a=1 to l01n=1 to 3) The fluorine compounds having the above reactive organic functional groups are preferred examples of fluorine compounds in the present invention, and the present invention is not limited to these examples. The compounds exemplified above and other fluorine compounds are currently commercially available and can be easily obtained from the market, and any of them can be used in the present invention.

The organic polyisocyanate used in the present invention is
It is a compound having at least two isocyanate groups in an aliphatic or aromatic compound, and has been widely used as a synthetic raw material for polyurethane resins.

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(phenylisocyanate), shrylene 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-methylenebis(cyclohexyl isocyanate), 1.5-tetrahydronaphthalene diisocyanate, etc.Furthermore, adducts of these organic polyisocyanates with other compounds, such as the following structural formula: There are things that can be mentioned,
Not limited to these.

C0NH(C)la)aNc.

ONC(C)I2) sN Enter C0NH (C1h) 5NcO To OCH.

The modifier of the present invention combines a fluorine compound having a reactive organic functional group as described above and an organic polyisocyanate as described above so that the reactive organic functional group and the isocyanate group are bonded together so that no isocyanate group remains after the reaction. , preferably at a functional group ratio of 1:1, in the presence or absence of an organic solvent and a catalyst, at a temperature of about 0 to 150°C, preferably 20 to 80°C, for about 10 minutes to 3 hours. can be easily obtained by

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,
Examples include pentane, hexane, cyclohexane, heptane, octane, mineral spirit, petroleum ether, gasoline, benzene, toluene, xylene, chloroform, carbon tetrachloride, chlorobenzene, perchloroethylene, trichlorethylene, and the like.

When the modifier of the present invention obtained as described above is produced using an organic solvent, it may be separated from the organic solvent, or it 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 fluorine compound undergo an addition reaction. For example, it has been revealed that when the reactive organic functional group is an amino group, the two are bonded through a urethane bond, and the compound is substantially free of free isocyanate groups.

In the second aspect of the present invention, the resins used as the resin modified with the modifier of the present invention are various conventionally known resins, and any of these conventionally known resins can be used, for example, Vinyl chloride resin, vinylidene chloride resin, vinyl chloride/vinyl acetate/vinyl alcohol copolymer resin, alkyd resin, epoxy resin, acrylonitrile-butadiene resin, polyurethane resin, polyurea resin, nitrocellulose resin, Examples include polybutyral resins, polyester resins, fluorine resins, melamine resins, urea resins, acrylic resins, polyamide resins, etc., and particularly preferred ones have urea bonds, urethane bonds, etc. in their structures. It is a polyurethane resin with Any of these resins can be used alone or as a mixture, and may be in the form of a solid solid, a solution in an organic solvent, or a dispersion.

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 the case of a paint form, the concentration of the resin is preferably about 1 to 50% by weight, and the modifier can be used in a proportion of about 1 to 100 parts by weight per 100 parts by weight of the resin.

(Function/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, and depending on the type of resin to be modified, the inherent properties of those resins can be modified. While maintaining various properties such as strength, flexibility, electrical, chemical, and physical properties, the surface properties of molded products formed from the resin, such as stain resistance, water resistance, and Abrasion resistance, adhesion resistance, heat resistance, etc. can be significantly improved, and the friction coefficient of molded products can be significantly reduced.

In addition, the modifier of the present invention is such that the modifier in the molded product is
Because the modifiers are integrated with each other or with the resin by polar groups such as urethane bonds and urea bonds, for example by hydrogen bonds, the additives are absorbed into the surface of the molded product over time, as in conventional lubricants. This solves the problem of bleed and causing various problems, and therefore a large amount of the modifier can be incorporated into the molded product, and as a result, the surface properties of the molded product can be further improved.

Next, the present invention will be explained in more detail by giving Examples, Usage Examples, and Comparative Examples. Note that parts and percentages in the text are based on weight.

Reference Example 1 (Production example of modifier) Adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Fukasei Co., Ltd., NC0% 23.5)
While thoroughly stirring 52 parts at 60° C., 80 parts of a fluorinated alcohol having the structure shown below was gradually added dropwise thereto to react, yielding 129 parts of a colorless and transparent liquid modifier (Ml).

H(CF2(:F2) sol According to the infrared absorption spectrum of this modifier, 2270
No absorption due to free isocyanate groups at /cm was observed, and an absorption band due to -CF2- groups was observed at 1190/cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

Reference Example 2 (Manufacturing Example of Modifier) Adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate 1 manufactured by Nippon Polyurethane, N00% 12°5, solid content 75%) 1
While thoroughly stirring 20 parts at 50° C., 171 parts of a fluorinated alcohol having the structure shown below is gradually added dropwise to the mixture for reaction.

CF3(CFzGh) 3011 After the reaction was completed, 251 parts of a transparent liquid modifier (Ml) was obtained.

According to the infrared absorption spectrum of this modifier, 2270
No absorption due to free isocyanate groups at /cm was observed, and an absorption band due to -CF2- groups was observed at 1190/cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

Reference Example 3 (Manufacturing Example of Modifier) 186 parts of an adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (Takenate D11ON, manufactured by Takeda Pharmaceutical, NC 0% 11.5, solid content 75%) were mixed at room temperature. While stirring, 258 parts of a fluorinated alcohol having the structure shown below was gradually added dropwise to the mixture for reaction.

After adding 2 parts of CF3 (CF20F2) 3 GHzc) I2SH, 384 parts of a transparent liquid modifier (M3) was obtained.

According to the infrared absorption spectrum of this modifier, 2270
No absorption due to free isocyanate groups at /cm was observed, and an absorption band due to 10F2- groups was observed at 1190/cm.

Therefore, the main structure of the above modifier is estimated to be the following formula.

(X -5CH2C)12 (CF2CF2) 3CF
3) Example 4 (Preparation of resin solution) 150 parts of polybutylene adipate having a molecular weight of 2,000 and 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 voids/
A polyurethane resin solution (solid content 35%) at 20°C was obtained. To 100 parts of this polyurethane resin solution was added a modifier (Ml
) was added to obtain a modified resin solution (URI).

Example 5 (Preparation of resin solution) In place of the modifier (Ml) in Example 4, a modifier (Ml) was used.
A modified resin solution (UR2) was obtained in the same manner as in Example 4 except that Example 1) was used.

Example 6 (Preparation of resin solution) In place of the modifier (Ml) in Example 4, a modifier (M
A modified resin solution (UR3) was obtained in the same manner as in Example 4 except that Example 3) was used.

Application example 1 Using the three 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 the coefficient of static friction and surface When the condition was determined, the results shown in Table 1 below were obtained. Note that Comparative Example 1 is a case where a resin solution before modification was used.

γ 1-” A B CD EURI 9
1.7 568 126 0.123 0UR294,
35611350,1190UR397,057312
50,1080 Comparative Example 1 88.0 555 1:11
0.635 0A, 100% modulus (g/cd
) B: Breaking strength (g/cm'') C: Tear strength (Kg/cm) D: Static FIJ coefficient (μk) E: Surface condition The static friction coefficient was measured using a sliding tester (Toyo Seiki type). This is a measured value, and the surface state is the state when the film was left for 5 days after film formation, and 0 indicates no change.

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 7 (Modification of resin) While stirring 200 parts of acrylic polyol (Hytaloid 3001, manufactured by Hitachi Chemical, solid content 50%), 5 parts of modifier M1 and 5 parts of butyl acetate were added, and a modified resin solution (ARI) was added. Obtained.

Example 8 (Modification of resin) In place of the modifier (Ml) in Example 7, a modifier (M
A modified resin solution (AR2) was obtained in the same manner as in Example 7 except that Example 2) was used.

Example 9 (Modification of resin) In place of the modifier (Ml) in Example 7, a modifier (M
A modified resin solution (AR3) was obtained in the same manner as in Example 11 except that Example 3) was used.

Application example 2 Using the above modified resins ARI to AR3, the following formulations were kneaded using three rolls to prepare three types of paints, which were coated on a zinc phosphate treated steel plate to a dry film thickness of 40 to 45 μm. A coating film was formed by coating and drying.

Modified resin 63 parts titanium white
35 parts Takenate D-11O
N 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. Note that Comparative Example 1 is a case where a resin solution before modification was used.

~J 2 - ”'ABCDE (a) (b) ARI 86 H-2HO○ 2.6 0AR2
87H-2HOO1,90 AR388)1-2HOO1,30 Comparative example 1 85 H-2)1 △Δ35.4
0A; Gloss (60 degree reflection) B: Pencil hardness C; Stain resistance D; Abrasion resistance ((:5-10, 500g, mg) E
:Surface condition: Stain resistance is determined by lipstick (a) and oil-based felt-tip pen (b)
This is the result of writing letters on the paint film with , leaving it at 30℃ for 24 hours, and then wiping it off with a cloth. O indicates that no contamination remains.
indicates that a slight amount of contamination remains. Abrasion resistance (mg) is an ASTM abrasion resistance test, and is a value measured using CSTO as a wheel, applying a load of 500 g, and rotating at 1,000 revolutions.The surface condition was measured after being left for 5 days after film formation. O indicates no change.

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 URI to OR3 obtained in the above examples were each coated on a 15 μm thick polyester film using a reverse roll coater so that the dry thickness was 1 μm, and the solvent was added. It was dried to form a heat-resistant layer. Next, a magnetic layer was formed on the opposite surface using a conventional method from a dispersion containing CO-containing -Fe 203 and a resin consisting of a normal polyurethane resin and a vinyl chloride copolymer resin, and was cut into a predetermined width. Three 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.

'A B CD E F Comparative example 1 0
．． 51 Yes Yes Yes Yes Defective [I R10
,21 None None None None Good U R20,20
Cum None None None Good UR30,20@
None None None Good The coefficient of friction (A) is the value (μk) measured between the magnetic layer and the molded product. noise (B), horizontal jitter (C), and irregular winding during fast forwarding of the tape (D) Ez.

The wear condition (E) of the magnetic layer is observed. 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 10 (Preparation of resin solution) The modifier obtained in Example 1 was added to 100 parts of a methyl ethyl ketone solution (solid content 30%) of vinyl chloride/vinyl acetate/vinyl alcohol copolymer resin (S-LEC A, manufactured by Block Chemical). 3 parts of (Ml) were added to obtain a modified resin solution (VRI).

Example 11 (Preparation of resin solution) In place of the modifier (Ml) in Example 1O, the modifier (
A modified resin (VH2) was obtained in the same manner as in Example 1O except that M2) was used.

Example 12 (Preparation of resin solution) In place of the modifier (Ml) in Example 10, the modifier (
A modified resin (VH3) was obtained in the same manner as in Example 1O except that M3) was used.

Usage example 4 Fe2Q3 with COO too part Any one of the above resin solutions VRI to VH3 (30% solution)
20 parts polyester type polyurethane resin solution (Rezamin ME12, manufactured by Dainichiseika Industries)
54 part powder (lecithin)
1 part carbon black 5
Part nitrocellulose 6 parts Methyl ethyl ketone 270 parts The above ingredients were mixed, kneaded in a ball mill for 50 hours, and further coronated to give 8 parts.
The mixture was further kneaded for 3 hours, and the kneaded mixture was passed through a filter to obtain a dispersion of three types of magnetic particles.

The three types of dispersions obtained above were coated on polyester films each having a thickness of 15 μm using a reverse roll coater to a thickness of 5 μm, and after drying the solvent, using a super calendar roll. The surfaces 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.

γ 4 'A B CD E F Comparative Example 10.
29 Minorities Not Available Not Available Japanese Food V R10,20
None None None None Good VR R20,13 None
None t#, None Good VR30, 2, 1 None
None None None Good The coefficient of friction (A) is the value measured between the magnetic layer and the support (base film) (μk)
The other performance was tested as a videotape, and the tape squeaked when it was run 200 times (B), jitter lateral shaking (C), and irregular winding during fast forwarding of the tape (D)
and the state of wear (E) of the magnetic layer was observed. 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 FJ coefficient of the magnetic layer and exhibits excellent running characteristics.

Claims (1)

[Scope of Claims] A resin modifier, which is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate, and is characterized in that it has substantially no free isocyanate groups. (2) A resin characterized in that a modifier, which is a reaction product of a fluorine compound having a reactive organic functional group and an organic polyisocyanate and has substantially no free isocyanate groups, is added to the resin. denaturation method.