JPH02616A - Polyurethane resin - Google Patents

Abstract

PURPOSE:To obtain a silicon-modified polyurethane resin excellent in nonstickiness, blocking resistance and flexibility by incorporating a siloxanepolyol component as at least a part of the polyol component or chain extender component contained. CONSTITUTION:In the production of a polyurethane resin by mixing a polyol component with a polyisocyanate component and a chain extender component, a siloxanepolyol component of formula I and/or formula II (wherein R is an alkyl; R' is H or a 1-15C alkyl; k=1-250; l=0-5; n in formula I is 1-3; and n in formula II is 2-3) is used as at least a part of the polyol component or the chain extender component. This resin has excellent solvent solubility and can give a film of excellent flexibility and has nonstickiness, blocking resistance, etc., at high temperature, so that it is useful as a binder for forming a magnetic layer of a magnetic recording medium; a binder for, e.g., a back coat formed on its back, a transfer film, etc; a material for synthetic leather; a fiber coating agent; a material for forming a release layer of a release paper, etc., or a binder for a coating agent and a printing ink.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to polyurethane resins, and more specifically,
The purpose of the present invention is to provide a silicone-modified polyurethane resin that has excellent non-adhesive properties, anti-blocking properties, and flexibility.

(Prior Art) Polyurethane resins have conventionally been widely used as various coating agents, binders for paints, inks, etc., films, molded articles, etc., and polyurethane resins suitable for each use have been proposed.

These polyurethane resins are basically obtained by reacting polyol components, polyisocyanate components, and chain extenders if necessary, and polyurethane resins with various physical properties are produced depending on the type and combination of these components. Resin is provided.

(The invention or the problem the problem is being solved) However,
Regarding the uses of polyurethane resins, for example, there are cases where non-adhesion to thermal heads and anti-blocking properties between films are required, such as heat-resistant layers of heat-sensitive recording materials and magnetic recording media. Sufficient flexibility is also typically required to form the coating.

However, in order to provide high non-adhesive properties, it is necessary to introduce aromatic components and many polar bonds into the polyurethane chain, which often results in a sacrifice of flexibility.

Therefore, there is a demand for the development of a polyurethane resin that has excellent high-temperature non-adhesive properties, anti-blocking properties, etc., as well as extremely excellent flexibility.

As a result of intensive research in order to solve the above-mentioned drawbacks of the prior art and to meet the above-mentioned needs, the present inventor has found that one object of the present invention can be achieved by forming a polyurethane resin using a specific polyol component. I found out that.

(Means for Solving the Problems) That is, the present invention provides a polyurethane resin containing a polyol component, a polyisocyanate component, and optionally a chain extender component, in which at least a part of the polyol component or the chain extender component is , a polyurethane resin characterized by being a siloxane polyol component represented by the following formulas (1) and/or (2).

RR CH20H (1) RRR However, R in the formula is an alkyl group, R' is a hydrogen atom or a C3 to C5 alkyl group, k = 1 to 250,
X=O to 5, m=o to 50, n in formula (1) is an integer of I to 3, n in formula (2) is 2 to 3
is an integer.

(Function) By bonding pendant polysiloxane bonds to the main chain of the polyurethane resin, the polyurethane resin maintains the excellent flexibility of the polyurethane resin and has excellent non-stick properties and anti-blocking properties. is provided.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments of the present invention.

The polyurethane resin used in the present invention and having pendant groups of the siloxane compound of the above formula (1) and/or (2), which mainly characterizes the present invention, is a polyol, a polyisocyanate, and optionally a chain extender, etc. When reacting to obtain a polyurethane resin, the above formula (1
) and/or (2).

The siloxane compounds of formulas (1) and (2) are currently commercially available and can be easily obtained manually from the market,
Any of these can be used in the present invention. Further, an intermediate obtained by reacting a siloxane compound as described above with a polyisocyanate as described below in such a manner that at least one of the reactive group of the siloxane compound or the isocyanate group of the polyisocyanate group remains, such as a bifunctional siloxane compound. An intermediate obtained by reacting a siloxane compound with a polyfunctional polyinsyanate enriched with incyanate groups, or conversely, an intermediate obtained by reacting a siloxane compound enriched with reactive groups can also be used in the present invention.

As the polyol that may be used in combination with the siloxane compound of surface formula (1) and/or (2), any conventionally known polyol for polyurethane can be used. For example, it is preferable that the terminal group is a hydroxyl group and the molecular weight is polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether Examples include glycol, poly-ε-caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, and those containing an appropriate amount of polyoxyethylene chains in the above polyols.

Any conventionally known organic polyisocyanate can be used, but for example, 4,4'-diphenylmethane diisocyanate (MDI) is preferred.
), water-added MDI, inphorone diisocyanate, 1.3-xylylene diisocyanate, 1.4-xylylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 1.5-naphthalene diisocyanate, m - Phenyl diisocyanate.

Of course, p-phenylene diisocyanate and the like, or urethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines to form terminal isocyanates, can also be used.

As the chain extender, any conventionally known chain extender can be used; for example, preferred ones include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 1. Examples include 2-propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, decamethylene diamine, isophorone diamine, m-xylylene diamine, hydrazine, and water.

Among the polyurethane resins containing pendant siloxane compounds obtained from the above-mentioned materials, particularly preferred are those in which the pendants of the siloxane compound account for about 1.0 to 50% by weight in the polyurethane resin molecule; Compound pendant is approximately 1.0J
If it is less than 1% by weight, the desired objectives of the present invention such as non-adhesiveness and anti-blocking properties will not be sufficiently exhibited, while if it exceeds 1% by weight, the resulting polyurethane resin will have insufficient flexibility. This is not desirable.

Moreover, the preferable ones have a molecular weight of 20,000 to 500,000, and the most preferable ones have a molecular weight of M2 to 250,000.

Further, in the present invention, the above-mentioned siloxane compound and polyisocyanate are reacted in an isocyanate-rich state to form a polyurethane resin having at least one free isocyanate group, which is then used as another film-forming resin 1.
It can also be used in combination with fingers as a modifier for them.

The polyurethane resin of the present invention containing the above-mentioned siloxane compound as a pendant can be easily obtained by a conventionally known manufacturing method. These polyurethane resins may be prepared without a solvent or in an organic solvent, but from a process standpoint, by preparing them in an organic solvent, the resulting solution can be used as is for various purposes. It is advantageous because it can be used.

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, and acetone. , cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isobrobyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichlorethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. can also be used.

Although the polyurethane resin of the present invention as described above has excellent non-adhesive properties and anti-blocking properties, it is easily soluble in various organic solvents and can form an excellent flexible film.

Therefore, binders for forming magnetic layers of magnetic recording media such as magnetic tapes, back coats formed on the back surfaces thereof,
Extremely useful as a binder for transfer films, etc. Formation of heat-resistant layers to prevent adhesion of thermal heads, formation of release layers for synthetic leather materials, fiber coating agents, surface treatment agents, release papers, etc., binders for paints, printing inks, etc. Appointed to.

Next, one example of the use of the polyurethane resin of the present invention will be described by citing the formation of a heat-resistant layer of a heat-sensitive recording material such as a heat transfer film.

A thermal recording material is a material in which a transfer ink layer or a sublimation transfer dye layer is provided on one surface of a base sheet such as a polyester film, and the ink layer or dye is transferred to the transfer material by heating from the back side in an imagewise manner with a thermal head. A monochrome or multicolor image is formed by using a thermal head, and when a thermal head is used for transfer, the thermal head sticks to the back surface, causing various troubles.

The polyurethane resin of the present invention has excellent flexibility and also has excellent non-stick properties especially at elevated temperatures.
It is ideal for such purposes. Of course, this example is just one
These are examples, and the uses of the polyurethane resin of the present invention are not limited to the above examples.

For forming the heat-resistant layer, it is preferable to use a paint formed by dissolving or dispersing the polyurethane resin of the present invention alone or in a mixture with other resins in the medium as described above. The total film-forming resin concentration in the paint is about 10 to 55
The polyurethane resin containing the siloxane compound of the present invention as a pendant can be used in an amount of about 1 to 100 parts by weight per 100 parts by weight of these film-forming resins.

Various film-forming resins known in the art can be used in combination as the pattern-forming resin. For example, vinyl chloride resin, vinylidene chloride resin, vinyl chloride/vinyl acetate/vinyl chloride resin, etc. Vinyl alcohol copolymer resin, alkyd resin, epoxy resin, acrylonitrile-butadiene resin, polyurethane resin, polyurea resin, nitrocellulose resin, polybutyral resin, polyester resin, fluorine resin, melamine resin , urea resins, acrylic resins, polyamide resins, etc. In particular, when the polyurethane resin having the siloxane compound group of the present invention as a pendant has a free isocyanate group, in its structure,
Resins having reactive groups capable of reacting with isocyanate groups are preferably used. These resins can be used alone or as a mixture, and can be used as a solution or dispersion in an organic solvent.

As long as the above-mentioned components are essential components, the paint for forming a heat-resistant layer may contain other subcomponents other than the above, such as pigments, extender pigments,
Optional additives such as plasticizers, antistatic agents, surfactants, lubricants, crosslinking agents, anti-aging agents, stabilizers, foaming agents, and antifoaming agents may be included.

The method of forming the heat-resistant layer itself may be the same as any conventionally known method, and it is preferably formed to a thickness of about 0.1 to 10 μm.

In addition, any conventionally known base sheet can be used, for example, polyester film, polypropylene film, cellulose triacetate film, cellulose diacetate film, polycarbonate film, etc. with a thickness of 5 to 50 μm can be used arbitrarily. I can do it.

The heat-sensitive recording material may be prepared by any known method, except for the use of polyurethane resin as described above to form the heat-resistant layer.
For example, the heat-sensitive recording layer can be formed from a conventionally known binder resin, a dye or pigment, an organic solvent, and various necessary additives according to a conventionally known method.

For example, as the binder resin, a resin such as the above-mentioned film-forming resin can be used, as the organic solvent, the above-mentioned organic solvent can be used, as the additive, the above-mentioned additive can be used, and as the dye or pigment, for example, , azo-based, phthalocyanine-based, quinacridone-based, and polycyclic pigments, and inorganic pigments such as carbon black, iron oxide, yellow lead, and cadmium sulfide.As dyes, various conventionally known dyes and Sublimable dyes, disperse dyes, etc. can be used.

(Effects) The polyurethane resin obtained as described above has excellent solvent solubility, provides an excellent flexible film, and has excellent high temperature non-stick properties, anti-blocking properties, etc. Therefore, it is useful for various uses as mentioned above.

(Example) Next, the present invention will be described in more detail by giving examples, comparative examples, and usage examples. Note that parts and percentages in the text are based on weight.

CII+ (:H3Cll3 CIh0
150 parts of polydimethylsiloxane polyol having the above structure (molecular weight 5,200) and 12 parts of 1,4-butanediol were added to 200 parts of methyl ethyl ketone. and 50 parts of dimethylformamide, and heated at 60°C.
While stirring well, 42 parts of water-added MDI dissolved in 128 parts of dimethylformamide was gradually added dropwise.
After the dropwise addition was completed, the mixture was reacted at 80° C. for 5 hours to obtain a polyurethane resin solution of the present invention.

This solution had a solid content of 35% and a yield of 16,500 cps (25°C).
) had a viscosity of

The film obtained from this solution has a breaking strength (kg/
crn”) 360, elongation at break (%) 350, and softening point was 92°C.

Garden ±1 CH3C113CH3 C11311J13C1+3
(:H20H (K is the value at which the molecular weight is 5,200) 75 parts of polydimethylsiloxane polyol having the above structure (molecule i 5..200), polybutylene adipate (molecular weight 2.000) 75 Part and 1.4
- Dissolve 15 parts of butanediol in a mixed solvent of 250 parts of methyl ethyl ketone and 50 parts of dimethyl formamide, and add 56 parts of water with stirring at 60°C.
was dissolved in 110 parts of dimethylformamide was gradually added dropwise, and after the addition was completed, the reaction was carried out at 80° C. for 5 hours to obtain a polyurethane resin solution of the present invention.

This solution has a solid content of 35% and a yield of 31,000 cps (25°C).
) had a viscosity of

The film obtained from this solution has a breaking strength (kg/c
), the elongation at break (%) was 400, and the softening point was 105°C.

Five points - DanC113(:113CH3[:2115(:lb+Si
O(Sin) xsi (to 112) 3 (0(41
2G(:II□)20HCII3Ctl+ [:11
3 GH2011 (K has a molecular weight of 4.50
This value is 0. ) Polydimethylsiloxane polyol having the above structure (molecule fi 4,500) 4
parts, polybutylene adipate (molecules [2,000) 1
46 parts and 10 parts of 1,4-butanediol were dissolved in a mixed solvent of 150 parts of methyl ethyl ketone and 100 parts of dimethylformamide, and 46 parts of
7 parts of water-added MDI dissolved in 134 parts of dimethylformamide was gradually added dropwise until the addition was complete. A polyurethane resin solution of the present invention was obtained by reacting at &80°C for 6 hours.

This solution had a solid content of 35% and a power output of 45,0000 cps (at 25°C).
) had a viscosity of

The film obtained from this solution has a breaking strength (kg/
crn”) 450, and elongation at break (%) 41o.
However, the softening point was 90°C.

4 parts of polydimethylsiloxane polyol having the above structure (molecule i: 4,800), polybutylene adipate (molecule i: 2,000) 146 parts and 10 parts of 1,4-butanediol were dissolved in a mixed solvent of 150 parts of methyl ethyl ketone and 100 parts of dimethylformamide.
A solution of 46 parts of water-added MDI dissolved in 134 parts of dimethylformamide was gradually added dropwise while stirring well at 80°C, and after the dropwise addition was completed, the reaction was carried out at 80°C for 6 hours to obtain a polyurethane resin solution of the present invention.

This solution had a solid content of 35% and a yield of 48,000 cps (at 25°C).
) had a viscosity of

The film obtained from this solution has a breaking strength (kg/c
d) 420, had an elongation at break (%) of 430, and a softening point of 95°C.

Example 1 A polyurethane resin solution of the present invention was obtained in the same manner as in Example 1 except that the same amount of the following siloxane compound was used in place of the siloxane compound in Example 1.

(K is the value at which the molecular weight is 5.200.) This solution had a solids content of 35% and a viscosity of 48.0 OO cps (25° C.).

The film obtained from this solution has a breaking strength (kg/
cr rr+') 420, elongation at break (%) 430, and softening point 95°C.

Example 1 A polyurethane resin solution of the present invention was obtained in the same manner as in Example 2 except that the same amount of the following siloxane compound was used in place of the siloxane compound in Example 2.

(K is the value at which the molecular weight is 5.200.) This solution had a solids content of 35% and a viscosity of 48.0 OO cps (25° C.).

The film obtained from this solution has a breaking strength (kg/c
It had an elongation at break (%) of 430, and a softening point of 95°C.

EXAMPLE 5 A polyurethane resin solution of the present invention was obtained in the same manner as in Example 3 except that the same amount of the following siloxane compound was used in place of the siloxane compound in Example 3.

(K is the value at which the molecular weight is 5,200.) This solution had a solids content of 35% and a viscosity of 48.0 OO cps (25° C.).

The film obtained from this solution has a breaking strength (kg/c
m'') was 420, elongation at break (%) was 430, and the softening point was 95°C.

A polyurethane resin solution of the present invention was obtained in the same manner as in Example 4 except that the same amount of the following siloxane compound was used in place of the siloxane compound in Example 4.

CI+3(:)13 C113 C1L+5iO(SiO)kSi(Cll□), (
OC++2CIICH□)311CI3CI+3 [
:H30tl (K is the value at which the molecular weight is 5,200.) This solution had a solid content of 35% and a viscosity of 48.0OOcps (25°C).

The film obtained from this solution has a breaking strength (kg/
crn') 420, elongation at break (%) 430, and softening point 95°C.

■Pine example↓ 150 parts of polybutylene adipate (molecular weight 2,000) and 15 parts of 1,4-butanediol were dissolved in a mixed solvent of 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide, and the mixture was stirred at 60°C. A solution of 62 parts of water-added MDI dissolved in 171 parts of dimethylformamide was gradually added dropwise, and after the dropwise addition was completed, the mixture was reacted at 80° C. for 6 hours.

This solution has a solid content of 35% and a yield of 32,000 cps (25°C).
) had a viscosity of

The film obtained from this solution has a breaking strength (kg/c
rn') 450, elongation at break (%) 480, and softening point was 102°C.

In addition, the softening point in the above is determined by cutting the film into strips,
Attach a male end to the bottom of the film to give a weight of 450 g/cm" and hang it in a gear oven, then heat it at 2°C/l.
The temperature was raised at a rate of 1 inch, and the temperature was determined as the temperature at which the elongation of the film suddenly increased or the film was cut.

Comparative Example 1 Silicone resin (S-841) 10 manufactured by Shin-Etsu Chemical Co., Ltd.
0 parts and 1 part of catalyst (PL-7) were mixed with 1.000 parts of toluene.
A silicone resin coating solution was prepared.

Usage Examples 1 to 8 and Comparative Usage Examples 1 to 3 A paint consisting of the following ingredients was prepared and applied to the back side of a polyester film with a thickness of 15 μm on which a heat-sensitive edge layer had been formed in advance. It was coated with a gravure coater to a thickness of 0.5 μm, and the solvent was dried in a drier to form a heat-resistant layer. This was cut to a predetermined size of 11 to prepare a heat-sensitive recording material using the polyurethane resin of the present invention and a heat-sensitive recording material for comparison.

Resin solution of Example 1 100 parts Methyl ethyl ketone 100 parts History ■ Example Resin solution of Example 2 100 parts Methyl ethyl ketone 100 parts Resin solution of Example 3 100 parts Methyl ethyl ketone 100 parts Implementation Resin solution of Example 4 Methyl ethyl ketone Use side 5 Resin solution of Example 5 Methyl ethyl ketone Part 1 Resin solution of Example 6 Methyl ethyl ketone 5 Resin solution of Example 7 Methyl ethyl ketone Hijo 1 Old Masumata 1 Resin solution of Comparative Example 1 Methyl ethyl ketone Hijo 1 Old Masumata Resin solution of Comparative Example 1 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts 100 5 parts talc methyl ethyl ketone 120 parts Evaluation The properties of the heat-sensitive recording materials obtained in Evaluation Use Examples 1 to 8 and Comparative Use Examples 1 to 3 are as shown in Table 1 below.

'X-1= Use example 1 Use example 2 Use example 3 Use example 4 Use example 5 Use example 6 Use example 7 198 Usage example 8 0.205 5 5 Comparative usage example 1 0.612 1 5 Comparative usage example 2 0.352 3 2 Comparative usage example 3
It is 0.195 5 2.

Claims (1)

[Claims] (1) In a polyurethane resin containing a polyol component, a polyisocyanate component, and optionally a chain extender component, at least a part of the polyol component or chain extender component is represented by the following formula (1) and/or (2). A polyurethane resin characterized by being a siloxane polyol component represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (However, R in the formula is an alkyl group, and R' is a hydrogen atom or an alkyl group of C_1 to C_5. and k=1 to 2
50, l=0 to 5, m=0 to 50, n in formula (1) is an integer of 1 to 3, n in formula (2) is 2
It is an integer between 3 and 3. )