JPH0649177B2 - Peeling treatment agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a release treatment agent, and more specifically, in a product using an adhesive such as an adhesive tape, an adhesive label, and an adhesive sheet, the adhesive surface is overlaid. The present invention relates to a releasable treatment agent capable of imparting releasability to the back surface of a base material such as a tape or the like or the surface of a release paper.

(Prior Art) Conventionally, as a release agent used for the above purpose, a polymer compound such as an acrylic acid-based, polyester-based or polyamide-based compound having a long-chain alkyl group bonded and an organopolysiloxane-based compound have been known. And is used for forming a release surface on the back surface of an adhesive tape or an adhesive sheet or on the surface of release paper. Among these, organopolysiloxane compounds are excellent in properties such as peelability and residual adhesiveness.

(Problems to be Solved by the Invention) Conventional organopolysiloxane compounds have the above-mentioned characteristics, but the peeling force is not appropriate, and since high temperature baking is required at the time of coating on a substrate, a thermoplastic group is used. There is a problem that it cannot be used for material films. Further, there is a defect that the adhesion to the base material is insufficient depending on the base material and it cannot be used for various kinds of base materials.

Further, since the peelable polysiloxane compound has a small critical surface tension, it cannot be written on the peeling surface, and a cissing phenomenon often occurs when a pressure-sensitive or heat-sensitive adhesive is applied to the peeling surface. However, there is a problem that a good coated surface cannot be formed.

Therefore, an object of the present invention is to provide a releasable treatment agent which can be baked at a low temperature and can be applied to a thermoplastic resin film or the like.

Another object of the present invention is to have no selectivity for the substrate,
It is an object of the present invention to provide a release treatment agent capable of forming a release surface on any base material.

Still another object of the present invention is to provide a releasable treatment agent capable of forming a releasable surface on which a writable aqueous ink or oily ink can be written.

(Means for Solving Problems) The above object is achieved by the present invention described below.

That is, the present invention relates to a release treatment agent containing a polyurethane or polyurea resin having a siloxane segment in the side chain, and a residue of the siloxane polyol in which the side chain is represented by the following formulas (1) and / or (2). It is a peeling processing agent characterized by being.

(However, in the formula, R is an alkyl group, R ′ is a C _{1 to} C ₅ alkyl group, k = 1 to 250, 1 = 0 to 5, m = 0 to 50, in the formula (1) n is 1 to 3
And n in the formula (2) is an integer of 2 to 3. ) (Operation) By using a resin that has a specific siloxane segment in the side chain, a release surface that can be baked at low temperature, has no selectivity for the substrate, can be written with a pen, etc., and has an appropriate release force is formed. be able to.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

The polysiloxane compounds of the general formulas (1) and (2) are commercially available at present, and are easily available from the market.
Both can be used in the present invention.

Furthermore, a compound of the general formula (1) and / or (2) as described above and a polyisocyanate as described below are added to the hydroxyl group of the compound of the general formula (1) and / or (2) or the isocyanate group of the polyisocyanate group. Intermediate obtained by reacting so that at least one of them remains, for example, a compound obtained by reacting a compound of the general formula (1) and / or (2) with a polyfunctional polyisocyanate in an isocyanate group-rich state, or conversely Intermediates obtained by making the hydroxyl groups of the compounds of formula (1) and / or (2) rich and reacting can be used as well.

The resin having a siloxane segment used in the present invention has a group capable of reacting with these reactive groups at the terminal or in the middle of the main chain, using the compound represented by the general formula (1) and / or (2). It is obtained by modifying the resin or by using the compound of the general formula (1) and / or (2) as one component of the resin synthesis.

For example, a method of utilizing a hydroxyl group of the compounds of the general formulas (1) and / or (2) and reacting with a resin having a carboxylic acid group, an acid anhydride group, an isocyanate group, an epoxy group or the like at the terminal or in the middle of the main chain. Or a method of synthesizing a polyurethane resin, a polyurea resin or a polyester resin using the compound of the general formula (1) and / or (2) as a monomer.

Examples of the above-mentioned resin having a reactive group include polyurethane resin, polyurea resin, polyurethane polyurea resin, acrylic resin, copolymer of olefin and acrylic monomer, partially saponified product of polyvinyl acetate, vinyl acetate and other monomer. Saponified copolymer, epoxy resin,
Any conventionally known reactive resin such as a polyamide resin, a polyester resin and a cellulose resin can be used.

Of the various resins having the polysiloxane segment as described above, particularly preferred in the present invention are polyurethane-based resins and / or polyurea-based resins, and a polyurethane-based resin will be described in more detail as a representative example.

The polyurethane-based resin having a siloxane segment in the side chain is prepared by reacting a polyol, a polyisocyanate, and a chain extender to prepare a polyurethane-based resin. It is obtained by using the compound of 2).

As the polyol for polyurethane, any conventionally known polyol for polyurethane can be used. For example, as a preferred polyol, the terminal group is a hydroxyl group and the molecular weight is 30.
0 to 4,000 polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly -Ε-caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, and the like, and those containing an appropriate amount of polyoxyethylene chain in the above-mentioned polyol.

As the organic polyisocyanate, any conventionally known one can be used. For example, as a preferred one, 4,4'-diphenylmethane diisocyanate (MD
I), water-added MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m -Phenylene diisocyanate, p-phenylene diisocyanate, etc., or a urethane prepolymer obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines so as to become terminal isocyanates can of course be used.

As the chain extender, any conventionally known one can be used, but preferred examples thereof include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 1, 2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine, hydrazine, water and the like.

Any polyurethane-based resin containing a polysiloxane segment obtained from the above-mentioned material in the side chain can be used in the present invention, but the preferred one is that the polysiloxane segment accounts for about 0.2 to 70% by weight in the resin. Occupies about 0.2 of polysiloxane segment
If the amount is less than 10% by weight, the intended purpose of the present invention will not be achieved sufficiently, and if the amount exceeds about 70% by weight, problems such as deterioration of adhesion to the substrate will occur, which is not preferable.

Incidentally, the polyurea-based resin and the polyurethane polyurea-based resin can be obtained in the same manner by using the compounds of the general formulas (1) and / or (2) and the polyamine instead of all or part of the polyol in the above.

Further, a preferable one has a molecular weight of 20,000 to 500,000, and a most preferable one has a molecular weight of 20,000 to 250,000.

The polysiloxane segment-containing polyurethane resin as described above can be easily obtained by a conventionally known production method. These polyurethane-based resins may be prepared without solvent or may be prepared in an organic solvent, but in the process, by preparing in the organic solvent in which the peeling treatment agent is to be prepared, It is advantageous because it can be used to prepare a release treatment agent.

Preferred as such an organic solvent are 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 the like, and acetone. , Cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethylsulfoxide, perchlorethylene, trichloroethylene, methylcellosolve, butylcellosolve, cellosolve acetate and the like can also be used. Of course, the above organic solvents can be used as a mixed organic solvent.

By preparing a polyurethane resin in such an organic solvent, a polyurethane resin solution having a polysiloxane segment can be obtained, but the solid content thereof is the same or in the range of about 5 to 60% by weight by adding or removing another solvent. Is convenient. In the present invention, the polyurethane resin may be a solution which is sufficiently dissolved in an organic solvent, or may be a dispersion which is partially or entirely precipitated (hereinafter simply referred to as a solution).

The above-mentioned polyurethane resin solution itself is the release treatment agent of the present invention, and it can be used as it is, and further various additives, for example, known additives such as colorants, crosslinking agents, stabilizers, fillers and the like. Can be added arbitrarily.

In particular, a conventionally known releasing agent as one kind of additives, for example, wood powder, talc, silica, boron nitride, alumina, polyethylene resin powder, benzoguanamine resin powder, silicone resin powder, melamine resin powder, fluororesin powder,
Phenol resin powder and the like can be added in an amount of 0 and 200 parts by weight per 100 parts by weight of the siloxane segment-containing resin. Further, as the additive, a general thermoplastic or thermosetting resin can be used together.

The above examples are mainly for the polyurethane-based resin, but of course the same applies to the above-mentioned resins other than the polyurethane-based resin, by introducing a siloxane segment as a side chain into the resin, and similarly in the present invention as a peelable component. Can be used.

(Effects) According to the present invention as described above, by using a resin having a siloxane segment in the side chain, low-temperature baking is possible, there is no selectivity for the base material, and writing with a pen or the like provides an appropriate release force. A peeling surface having can be formed.

EXAMPLES Next, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on weight.

Reference Examples 1 to 8 and Comparative Reference Examples 1 and 2 Reference Example 1 (K is a value at which the molecular weight becomes 5,200.) 150 parts of polydimethylsiloxane polyol (molecular weight 5,200) having the above structure and 12 parts of 1,4-butanediol, 200 parts of methyl ethyl ketone and 50 parts of dimethyl. Dissolve in a mixed solvent with formamide, 60 ℃
While stirring well, 42 parts of water-added MDI dissolved in 128 parts of dimethylformamide was gradually added dropwise.
After the dropping was completed, the reaction was carried out at 80 ° C. for 5 hours to obtain a polyurethane resin solution.

The solution had a viscosity of 16,500 cps (25 ° C) at 35% solids.

The film obtained from this solution has a breaking strength (kg / cm
² ) It had a breaking elongation (%) of 350 and a softening point of 92 ° C.

Reference example 2 (K is a value at which the molecular weight becomes 5,200.) 75 parts of polydimethylsiloxane polyol (molecular weight 5,200) having the above structure, 75 parts of polybutylene adipate (molecular weight of 2,000) and 1,4-butanediol 1
5 parts was dissolved in a mixed solvent of 250 parts of methyl ethyl ketone and 50 parts of dimethylformamide, and 56 parts of water-added MDI dissolved in 110 parts of dimethylformamide was slowly added dropwise while stirring well at 60 ° C. After completion of the dropping, reaction was carried out at 80 ° C. for 5 hours to obtain a polyurethane resin solution.

The solution had a viscosity of 31,000 cps (25 ° C) at 35% solids.

The film obtained from this solution has a breaking strength (kg / cm
² ) At 460, the elongation at break (%) was 400 and the softening point was 105 ° C.

Reference example 3 (K is a value at which the molecular weight becomes 4,500.) 4 parts of polydimethylsiloxane polyol (molecular weight 4,500) having the above structure, 146 parts of polybutylene adipate (molecular weight 2,000) and 1,4-butanediol 10
Parts were dissolved in a mixed solvent of 150 parts of methyl ethyl ketone and 100 parts of dimethylformamide, and 47 parts of water-added MDI dissolved in 134 parts of dimethylformamide were gradually added dropwise with good stirring at 60 ° C. After the dropping was completed, the reaction was carried out at 80 ° C. for 6 hours to obtain a polyurethane resin solution.

The solution had a viscosity of 45,000 cps (25 ° C) at 35% solids.

The film obtained from this solution has a breaking strength (kg / cm
² ) 450, elongation at break (%) 410, softening point 9
It was 0 ° C.

Reference example 4 (K is a value at which the molecular weight becomes 4,800.) 4 parts of polydimethylsiloxane polyol (molecular weight 4,800) having the above structure, 146 parts of polybutylene adipate (molecular weight 2,000) and 1,4-butanediol 10
Parts were dissolved in a mixed solvent of 150 parts of methyl ethyl ketone and 100 parts of dimethylformamide, 46 parts of water-added MDI dissolved in 134 parts of dimethylformamide were gradually added dropwise while stirring well at 60 ° C. After the dropping was completed, the reaction was carried out at 80 ° C. for 6 hours to obtain a polyurethane resin solution.

The solution had a viscosity of 48,000 cps (25 ° C) at 35% solids.

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

Reference Example 5 A polyurethane resin solution was obtained in the same manner as in Reference Example 1 except that the following siloxane compound was used in the same amount instead of the siloxane compound in Reference Example 1.

(K is the value at which the molecular weight is 5,200.) This solution had a solid content of 35% and a viscosity of 48,000 cps (25 ° C.).

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

Reference Example 6 A polyurethane resin solution was obtained in the same manner as in Reference Example 2, except that the following siloxane compound was used in the same amount instead of the siloxane compound in Reference Example 2.

(K is the value at which the molecular weight is 5,200.) This solution had a solid content of 35% and a viscosity of 48,000 cps (25 ° C.).

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

Reference Example 7 A polyurethane resin solution was obtained in the same manner as in Reference Example 3 except that the following siloxane compound was used in the same amount instead of the siloxane compound in Reference Example 3.

(K is the value at which the molecular weight is 5,200.) This solution had a solid content of 35% and a viscosity of 48,000 cps (25 ° C.).

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

Reference Example 8 A polyurethane resin solution of the present invention was obtained in the same manner as in Reference Example 4, except that the following siloxane compound was used in the same amount instead of the siloxane compound in Reference Example 4.

(K is the value at which the molecular weight is 5,200.) This solution had a solid content of 35% and a viscosity of 48,000 cps (25 ° C.).

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

Comparative Reference Example 1 (Synthesis of Conventionally Known Polyurethane Resin) Polybutylene adipate 1 having an average molecular weight of about 2,000
50 parts and 10 parts of 1,4-butanediol are dissolved in a mixed organic solvent consisting of 120 parts of methyl ethyl ketone and 130 parts of dimethylformamide, and 47 parts of water-added MDI are dissolved in 135 parts of methyl ethyl ketone. A polyurethane resin solution was obtained in the same manner as in Reference Example 1 except for the above.

The solid content of this solution is 35%, 14,500 cps
It had a viscosity of (25 ° C).

Comparative Reference Example 2 Shin-Etsu Chemical Co., Ltd. Polysiloxane resin (trade name: KS-8)
41) 100 parts and accompanying solvent (trade name; PL-7) 1
Parts were dissolved in 1,000 parts of toluene to obtain a polysiloxane resin coating solution.

Examples 1 to 8 and Comparative Examples 1 and 2 100% modulus 60 kg / cm was used for the following release treatment agents.
^{2. On} one side of polyvinyl chloride film with a thickness of 50 μm,
A sample having a releasable coating layer was prepared by uniformly coating so as to have a coating amount of solid content of 0.6 g / m ² and heating and drying at 80 ° C. for 30 seconds. When the temperature was raised to a high temperature (100 ° C. or higher), the polyvinyl chloride film was softened and the shape of the film could not be maintained.

Acrylic pressure sensitive adhesive tape (made by Sekisui Chemical Co., Ltd.) with a width of 20 mm was pressure-bonded onto the coated base material prepared in this way with a rubber roller having a weight of 2 kg, and after 1 day at room temperature (20 ° C, 52% humidity) and at high temperature (40%).
The peel strength, residual adhesive strength, residual adhesive strength retention rate, detachability of the peelable coating layer, and writability with magic ink after standing for 3 days at ℃ and humidity of 90% or more) were measured, and the results are shown in Table 1 below. Indicated.

Example 1 Resin solution of Reference Example 1 100 parts Methyl ethyl ketone 250 parts Example 2 Resin solution of Reference Example 2 100 parts Fluororesin powder (Daikin Industries; Lubron L-2) 5 parts Methyl ethyl ketone 250 parts Example 3 Resin of Reference Example 3 Solution 100 parts Coronate L (addition product of trimethylolpropane and TDI) 2 parts Methyl ethyl ketone 250 parts Resin solution of Example 4 Reference Example 4 100 parts Coronate L 2 parts Silicone resin powder (Toshiba Silicone, Tospearl 120) 5 parts Methyl ethyl ketone 250 Parts Example 5 Resin solution of Reference Example 5 100 parts Methyl ethyl ketone 250 parts Example 6 Resin solution of Reference Example 6 100 parts Fluororesin powder (Daikin Industries; Lubron L-2) 5 parts Methyl ethyl ketone 250 parts Example 7 Reference Example 7 Resin solution 100 parts Coronate L (Trimethylo) 2 parts methyl ethyl ketone 250 parts Example 8 Resin solution of Reference Example 8 100 parts Coronate L 2 parts Silicone resin powder (Toshiba Silicone, Tospar 120) 5 parts Methyl ethyl ketone 250 parts Comparative Example 1 Comparative Reference Example 1 Resin solution of 100 parts Silicone oil (SH-200, Toray Silicone) 5 parts Methyl ethyl ketone 250 parts Comparative Example 2 Resin solution of Comparative Reference Example 100 100 parts Each evaluation was performed as follows.

Peeling force: An adhesive tape having a width of 20 mm is attached to the peelable coating layer, stored at 40 ° C. under a load of 20 g / cm ² for 24 hours, and then peeled by pulling at an angle of 180 ° at a speed of 300 mm / min. The force (g) required for the measurement was measured (20 ° C).

Residual adhesive force: The adhesive tape after the peeling force measurement was adhered to a stainless steel plate # 280, reciprocated once with a 2 Kg tape roller, and after 30 minutes, pulled at an angle of 180 ° at a speed of 300 mm / min and peeled off. The force (g) required for the measurement was measured (20 ° C).

Residual adhesive retention rate: Shows% of residual adhesive force when a clean adhesive tape that was not subjected to peeling resistance was adhered to stainless plate # 280, and the adhesive force (320g / 20mm) to the stainless plate was 100%. There is.

Detachability: The strippable film layer is subjected to a reciprocating test with a load of 50 g / cm ² for one reciprocation, and the sample is subjected to a detachability test of the detachable film layer.

Writability with Magic Ink: Characters were written with a commercially available oil-based Magic Ink on the peelable coating layer, and the presence or absence of ink repellency during writing was examined.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoko Goto 4-4-33 Nishi-Aoki, Kawaguchi City, Saitama Prefecture (72) Inventor Katsumi Kuriyama 1135-1, Kuri Shioma, Koshigaya City, Saitama Prefecture (56) References 54-71135 (JP, A)

Claims (3)

[Claims] 1. A peeling treatment agent containing a polyurethane or polyurea resin having a siloxane segment in a side chain, wherein the side chain is a residue of a siloxane polyol represented by the following formulas (1) and / or (2). A releasable treatment agent characterized by being present. (However, in the formula, R is an alkyl group, R ′ is a C _{1 to} C ₅ alkyl group, k = 1 to 250, 1 = 0 to 5, m = 0 to 50, in the formula (1) n is 1 to 3
And n in the formula (2) is an integer of 2 to 3. ) 2. The peeling treatment agent according to claim 1, further comprising a peeling substance. 3. The peeling treatment agent according to claim 1, which is an organic solvent solution.