JP2002179757A - Polyurethane composite resin - Google Patents

Abstract

(57) [Problem] To provide a material which can obtain an effect of improving adhesion / adhesion without using a halogen compound in a polyolefin material which has been difficult to adhere in the past. SOLUTION: A polyolefin and a polyurethane are chemically bonded to form a polyurethane composite resin, thereby obtaining a material having a high adhesion / adhesion improving effect to a polyolefin material. Further, these were used as a film-forming material for polyolefin, an adhesive and an adhesive, and a laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane composite resin obtained by chemically bonding a monool containing a hydrocarbon having 25 to 200 carbon atoms to a polyurethane. More specifically, the present invention relates to a film-forming material capable of exhibiting excellent adhesion to polyolefin, an adhesive material including a pressure-sensitive adhesive, and a polyolefin laminate using the same.

[0002]

2. Description of the Related Art Polyolefin-based materials such as polyethylene and polypropylene are used in a wide range of applications from the viewpoint of cost and workability. However, these resins have low compatibility with film-forming materials such as inks and paints, adhesives and adhesives due to the low polarity of the resin itself and the high crystallinity, and it is necessary to obtain sufficient adhesive strength. It was difficult.

As a method for solving these problems, a method in which chlorinated polypropylene is coated on an olefin surface and used as a primer (Japanese Patent Publication No. 7-79990) or the chloride is incorporated into a film forming material For example, a method for obtaining an effect of improving adhesion / adhesion has been widely used. However, in this method, special consideration is required for incineration after use, in that a halide is used.

In addition, a method in which an unsaturated carboxylic acid such as maleic anhydride is grafted onto polypropylene or polyethylene in the presence of a radical polymerization initiator, and a polyolefin compound partially having a polar moiety introduced therein is incorporated into the film-forming material. And so on. However, in this method, it is difficult to improve the introduction rate of maleic anhydride, and high adhesion
/ It was difficult to obtain an adhesion improving effect. Furthermore, it was not possible to efficiently produce a modified polyolefin having a high introduction rate.

[0005]

SUMMARY OF THE INVENTION The present inventor has proposed that a polyolefin and a polyurethane are chemically bonded to each other to form a polyurethane composite resin containing a polyolefin portion and a polyurethane portion. The present inventors have found that a high adhesion / adhesion improving effect can be obtained for a polyolefin material without using a modified polyolefin, and the present invention has been accomplished.

[0006]

Means for Solving the Problems The present inventor has proposed that the number of carbon atoms is 25 to
High adhesion to polyolefin materials by forming polyurethane composite resin by chemically bonding polyurethane material starting from hydroxyl group of monool (a) containing 200 hydrocarbons
/ It has been found that an effect of improving adhesion can be obtained.

That is, the present invention provides a polyurethane composite obtained by reacting a monool (a) containing a hydrocarbon having 25 to 200 carbon atoms, a polyfunctional isocyanate compound (b), and an alcohol (c) other than (a). About resin.

The present invention also relates to a film-forming material for polyolefin comprising the above-mentioned polyurethane composite resin.

The present invention also relates to a polyolefin adhesive comprising the polyurethane composite resin and a tackifier.

Further, the present invention relates to a laminate obtained by laminating the polyurethane composite resin on a polyolefin.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin monool (a) containing a hydrocarbon having 25 to 200 carbon atoms in the present invention has one hydroxyl group in one molecule and is a polyolefin such as polyethylene or polypropylene, or It has a linear or branched, saturated or unsaturated hydrocarbon group having 25 to 200 carbon atoms, such as polybutadiene.

Specifically, there are polyethylene monool, polypropylene monool, polybutadiene monool and the like, and these are not particularly limited even if they are primary, secondary and tertiary alcohols. However, in consideration of the reaction efficiency when converting to polyurethane and the effect of improving the adhesion / adhesion of the composite resin, primary alcohols are most preferable.

The number of carbon atoms in the hydrocarbon group contained in the monol (a) is preferably from 25 to 200, more preferably from 25 to 100.
When the number of carbon atoms is less than 25, properties as a polyolefin are not exhibited. On the other hand, if the number of carbon atoms exceeds 200, the properties of the polyolefin become too strong, and it is difficult to obtain the effect as a composite material.

The polyfunctional isocyanate compound (b) in the present invention is a compound having two or more isocyanate groups in one molecule. The isocyanate group of the isocyanate compound (b) reacts with the hydroxyl group of the monol (a) and the alcohol (c) to form a polyurethane bond. If the polyfunctional isocyanate compound (b) is listed,
For example, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, xylene diisocyanate, tolidine diisocyanate, dianisidine diisocyanate, isopropylidene bis (phenylisocyanate ) And other linear diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, norbornene diisocyanate and dicyclohexylmethane Cyclic aliphatic diisocyanates such as isocyanate, dicyclohexyl ether diisocyanate, and isopropylidenebis (cyclohexyl isocyanate); Methane triisocyanate, bis (diisocyanate-tolyl) 3 or more functional isocyanate compounds such as triphenylmethane, and polymers of the isocyanates, such as polyphenyl methane diisocyanate and the like.

Of these, the use of a diisocyanate compound is preferred because the molecular weight of the polyurethane part can be easily controlled.

The alcohol (c) other than (a) in the present invention is a compound containing one or more hydroxyl groups in one molecule. The alcohol (c) is a substance that forms the polyurethane portion together with the isocyanate compound (b). Alcohol (c) is a different element from monol (a). That is, while the monool (a) is a portion constituting the polyolefin portion of the polyurethane composite resin, the alcohol (c) is a component forming the polyurethane portion of the isocyanate compound (b).
Used to compose with. The alcohol (c) includes a polyfunctional alcohol (c-1) and a monofunctional alcohol (c-2). By using the polyfunctional alcohol (c-1), the molecular weight of the polyurethane portion and the urethane bond density can be reduced. It can be adjusted and the isocyanate end can be blocked or modified by the monofunctional alcohol (c-2).

The polyfunctional alcohol (c-1) which can be used as the alcohol (c) includes diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol and butylene glycol, glycerin and trimethylolpropane. Triols, such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, polyhydric alcohols such as sorbit, and further polycaprolactone, polyethylene glycol,
Polymerized polyols such as polypropylene glycol and polyester polyols are also included. Among these,
In particular, the use of diols is preferable because the molecular weight of the polyurethane portion can be easily controlled.

The monofunctional alcohol (c-2) which can be used as the alcohol (c) is not particularly limited as long as it contains one hydroxyl group in one molecule. Examples thereof include aliphatic monols such as methanol, ethanol, propanol, butanol, lauryl alcohol, and stearyl alcohol; aromatic monols such as phenol, naphthol and benzyl alcohol; and alkylene glycol ether monols such as propylene glycol monomethyl ether. .

In addition, the alcohol (c) can further modify the polyurethane portion by having another functional group other than a hydroxyl group. For example, for the purpose of introducing a double bond, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycerin divinyl ether, pentaerythritol tri (meta) ) Unsaturated alcohols such as acrylate, pentaerythritol trivinyl ether, trimethylolpropane di (meth) acrylate, trimethylolpropane divinyl ether, and divinylphenol can also be used. Similarly, hydroxycarboxylic acid for introducing a carboxyl group, hydroxyamine and its dehydrated lactone for introducing an amino group, glycidyl alcohol for introducing an epoxy group, and the like can be used.

Monool (a), polyfunctional isocyanate compound (b), and (a) when synthesizing polyurethane composite resin
The composition ratio of the alcohol (c) other than the above is important for controlling the ratio of the polyolefin portion and the polyurethane portion of the polyurethane composite resin. In addition, other alcohol (c) polyfunctional alcohol (c-1) and monofunctional alcohol (c-
The ratio of 2) is also important for controlling the molecular weight of the polyurethane part, and should be appropriately adjusted according to the intended molecular weight of the polyurethane part. However, in consideration of the stability over time of the polyurethane composite resin after the completion of the reaction, it is preferable that the remaining isocyanate groups are eliminated. For this reason, it is preferable that the total amount of the hydroxyl groups contained in the monol (a) and the alcohol (c) is added at least equivalent to the isocyanate of the isocyanate compound (b).

The preferred ratio of the polyolefin portion to the polyurethane portion of the polyurethane composite resin is such that the average carbon number of the polyurethane portion is 0.1% of the carbon number of the polyolefin portion.
When the ratio is 1 to 10 times, particularly when the ratio is 0.5 to 5 times, the characteristics of the polyurethane composite resin remarkably appear.

The synthesis of the polyurethane composite resin is performed by a known general polyurethane synthesis method, and is not particularly limited. In particular, the reaction temperature is such that the monol (a) melts,
Alternatively, it is preferable to carry out the reaction in a state of being dissolved by a solvent because the molecular weight of the urethane moiety can be easily controlled.

The reaction temperature during the synthesis of the polyurethane composite resin is from 60 to 200 ° C., preferably from 80 to 160 ° C.

When synthesizing a polyurethane composite resin,
Conventional known catalysts used for general urethanization, for example, metal compounds such as dibutyltin laurate, tin dioctylate, and lead dioctylate, triethylamine, N, N-
Amines such as dimethylbenzylamine and triphenylamine can be used as needed.

In synthesizing the polyurethane composite resin (A), a general radical inhibitor such as hydroquinone and triethylamine can be used for the purpose of protecting the gel from inadvertent gelation during the reaction.

Further, it reduces residual isocyanate,
Alternatively, known amines, carboxylic acids, and amino acids can be added as needed to control the molecular weight of the polyurethane portion.

The amines may be any of primary, secondary and tertiary amines, and are not particularly limited to monoamines, diamines, triamines and polyamines containing more amino groups.

As the carboxylic acids, monocarboxylic acids,
There is no particular limitation on dicarboxylic acids, tricarboxylic acids, or polycarboxylic acids containing more carboxyl groups.

In the present invention, the polyurethane composite resin is obtained as a solid or a viscous body at room temperature. If these are to be blended as a film-forming material and an adhesive, they may be dissolved in the film-forming material and used,
If it cannot be dissolved, it may be added in the form of fine particles.

The addition amount is 0.1 to 30% by weight, preferably 0.5 to 15% by weight in the medium to be added. When the addition amount is small, the effect of improving the adhesion / adhesion becomes thin, and when the addition amount is large, the obtained film forming material and adhesive become brittle.

The film forming material in the present invention includes gravure ink, flexographic ink, silk screen ink,
Offset ink, overprinting varnish, paint, primer, anchor coat, filling varnish, etc. are not particularly limited, and can be used for all applications. Particularly excellent effects are exhibited when used as a film ink (for front printing, back printing, and laminating), a primer, or an anchor coat.

The pressure-sensitive adhesive and the adhesive in the present invention include:
There is no particular limitation on the adhesive tape, laminating adhesive, filler and the like, and it can be used for all applications.

The tackifier in the present invention refers to a pressure-sensitive adhesive and other materials constituting an adhesive. For example, it refers to resins such as acrylic resin, polyester resin, urethane resin, synthetic rubber, natural rubber, rosin, tachyfire, and the like, and further modified products of these resins.

The laminate in the present invention refers to a laminate obtained by laminating a layer containing a polyurethane composite resin on a polyolefin by a method such as printing, coating, melt coating, or laminating. The lamination is not particularly limited, even if it is a single layer or a plurality of layers.

Examples of the polyolefin constituting the laminate in the present invention include low-density polyethylene, high-density polyethylene, and polypropylene. These are not limited to shapes such as a film, a sheet, and a molded product. Further, there is no limitation on the presence or absence of a strengthening treatment such as a stretching treatment or an easy adhesion treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, and a cleaning treatment. However, the effects of the present invention are:
It is best exhibited when the polyolefin is untreated and easily treated.

[0036]

The present invention will be specifically described below.

Example 1 Synthesis of Polyurethane Composite Resin Monool (a) and isocyanate compound (b) shown in Table 1 were charged into a 1-liter three-necked flask equipped with a cooling tube at the weight shown in Table 1, and 200 ml of toluene, 1 g of hydroquinone, and 0.5 g of tin dioctylate as a reaction catalyst were added, and the mixture was heated to 120 ° C. in an oil bath. After the reaction, it was confirmed that the residual isocyanate value was obtained by calculation from the respective composition ratios, and a polyfunctional alcohol (c-1) was further added as shown in Table 1. Furthermore, after confirming that the isocyanate value obtained by calculation from each composition ratio was obtained, the monofunctional alcohol (c-2) was further converted to 2-isocyanate.
An excess amount of propanol (more than 10 molar equivalents relative to the last isocyanate value) was added. After confirming that there was no residual isocyanate by an infrared absorption spectrum, the solvent was removed under reduced pressure to obtain a polyurethane composite resin.

To the obtained composite resin, 2-propanol was added to adjust the solid content to 25% by weight, and the mixture was dispersed or dissolved by a high-speed mixer.

In the table, the notation of alcohol (a) is, for example, C25
Represents that it is a polyethylene monol having an average carbon number of 25. Also. In parentheses after the weight is stated,
The number of moles of each material is shown. Further, the carbon number ratio is represented by a value of (average carbon number of urethane portion in one molecule) / (average carbon number of alkyl portion). Table 1---------------------No. Alcohol (a) Isocyanate (b) Alcohol (c- 1) Carbon number ratio −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1.1 C25 184g (0.5) HMDI 168g ( 1.0) EG 31g (0.5) 0.8 Example 1.2 C25 184g (0.5) HMDI 252g (1.5) EG 62g (1.0) 1.2 Example 1.3 C25 92g (0.25) HMDI 210g (1.25) EG 62g (1.0) 2.0 Example 1.4 C25 46g (0.13) HMDI 210g (1.25) EG 70g (1.13) 4.0 Example 1.5 C25 23g (0.06) HMDI 210g (1.25) EG 70g (1.19) 8.0 Example 1.6 C25 12g (0.03) HMDI 210g (1.25) EG 76g ( 1.22) 16.0 Example 1.7 C50 359g (0.5) HMDI 252g (1.5) EG 62g (1.0) 0.6 Example 1.8 C50 90g (0.13) HMDI 210g (1.25) EG 70g (1.13) 2.0 Example 1.9 C50 44g (0.06) HMDI 210g (1.25) EG 74g (1.19) 4.0 Example 1.10 C75 67g (0.06) HMDI 210g (1.25) EG 74g (1.19) 2.7 Example 1.11 C120 104g (0.06) HMDI 210g (1.25) EG 74g (1.19) 1.7 Example 1.12 C25 184g (0.5) IPDI 333g (1.5) EG 62g (1.0) 1.7 Example 1.13 C25 46g (0.25) IPDI 278g (1.25) EG 62g (1.0) 2.8 Example 1.14 C25 46g (0.13) IPDI 278g (1.25) EG 70g (1.13) 5.6 Example 1.15 C25 92g (0.25 ) HMDI 210g (1.25) HDO 118g (1.0) 2.7 Example 1.16 C25 92g (0.25) HMDI 210g (1.25) DEG 106g (1.0) 2.4 Example 1.17 C25 92g (0.25) HMDI 210g (1.25) TEG 245g (1.0) 2.7 Example 1.18 C25 92 g (0.25) HMDI 210 g (1.25) PEG 620 g (1.0) 4.9 Example 1.19 C25 92 g (0.25) HMDI 210 g (1.25) DCP 228 g (1.0) 4.0 Example 1.20 C25 92 g (0.25) HMDI 210 g (1.25) ) TCP 228g (1.0) 5.1 Comparative Example 1.1 C12 47g (0.25) HMDI 210g (1.25) EG 62g (1.0) 4.1 −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−− HMDI: hexamethylene diisocyanate, IPDI: isophorone diisocyanate, EG: ethylene glycol, HDO: hexanediol, DEG: diethylene glycol, TEG: triethylene glycol, PEG: polyethylene glycol ( n = 10), DCP: Dicaprolac , TCP: tricaprolactone Example 2 Evaluation of adhesion of polyurethane composite resin The composite resin synthesized in Example 1 and dispersed in 2-propanol (solid content: 25% by weight) was manufactured by Arakawa Chemical Co., Ltd.
(Solvent-type polyurethane), the addition amount (in terms of solid content) shown in Table 2 was mixed, and sufficiently stirred with a mixer. After stirring, biaxially oriented polypropylene film (untreated)
Then, coating was performed with a bar coater # 5 and drying with a dryer was performed.

After drying, the coated film was coated with Cellotape (registered trademark).
A peel test was performed. Cellophane tape peeling is evaluated in 5 steps,
5: Not peeled, 4: Partially peeled when strongly peeled, 3: All peeled when strongly peeled, 2: Partially peeled when weakly peeled, 1:
All peeled even if peeled weakly. Table 2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− No.Composite resin (A) Addition amount (wt%) Adhesion evaluation −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− and / etc etc Example 2.3 Example 1.3 2 5 Example 2.4 Example 1.4 2 4 Example 2.5 Example 1.5 2 3-4 Example 2.6 Example 1.6 2 3 Example 2.7 Example 1.7 2 4-5 Example 2.8 Example 1.8 25 Example 2.9 Example 1.9 25 Example 2.10 Example 1.10 2 4-5 Example 2.11 Example 1.11 2 3 Example 2.12 Example 1.12 25 Example 2.13 Example 1.13 25 Example 2.14 Example 1.14 2 4 Example 2.15 Example 1.15 25 Example 2.16 Example 1.16 25 Example 2.17 Example 1.17 25 Example 2.18 Example 1.18 2 4-5 Example 2.19 Example 1.19 25 Example 2.20 Example 1.20 2 4 Example 2.21 Example 1.2 0.3 3 Example 2.22 Example 1.2 15 Example 2.23 Example 1.2 20 4 Example 2.24 Example 1.2 35 3 Comparative Example 2.1 None 0 1 Comparative Example 2.2 Comparative Example 1.1 2 1 Comparative Example 2.3 PPCl 4 4 −−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−− PPCl: Chlorinated polypropylene toluene solution (Supercron 803 MW, manufactured by Nippon Paper Industries) The indicated amount is converted to solid content. Example 3 Evaluation of adhesion of polyurethane composite resin Synthesized in Example 1, The composite resin prepared by dispersing in 2-propanol (solid content 25% by weight) was
(Polypropylene-isoprene block copolymer) / Arakawa Chemical Co., Ltd. Alucon M (Tachyfire-based tackifier) was mixed in the adhesive composition shown in Table 3 (solid content basis) and sufficiently stirred with a mixer. After the completion of the stirring, a biaxially stretched polypropylene film (untreated) was coated with an applicator to a thickness of 30 μm, and dried at 150 ° C. for 10 minutes. After the drying, the silicone-treated release paper was overlaid and cut into a size of 25 mm in width and 50 mm in length. Furthermore, the release paper was removed, and the 25 mm long and 25 mm wide parts of the resulting adhesive surface were stuck on a SUS304 stainless plate with # 280 sandpaper, pressed back and forth with a 2 kg roll once and left for 20 minutes, then left at room temperature.
The 180 ° peel adhesive force was measured at a peel rate of 300 mm / min in an atmosphere of 25 ° C. and a relative humidity of 65%. Table 3--------------------------No. Composite resin (B) Addition amount (% by weight) Peel adhesion Force (kg / 25mm)---------------------------------------------------------------------------------------------------------------------------- 3.2 Example 1.2 2 2.8 Example 3.3 Example 1.3 2 2.2 Example 3.4 Example 1.4 2 1.6 Example 3.5 Example 1.5 2 1.1 Example 3.6 Example 1.6 2 0.8 Example 3.7 Example 1.7 2 1.9 Example 3.8 Example Example 1.8 2 2.3 Example 3.9 Example 1.9 2 2.2 Example 3.10 Example 1.10 2 1.8 Example 3.11 Example 1.11 2 1.0 Example 3.12 Example 1.12 2 2.3 Example 3.13 Example 1.13 2 2.4 Example 3.14 Example 1.14 2 2.0 Example 3.15 Example 1.15 2 2.7 Example 3.16 Example 1.16 2 2.2 Example 3.17 Example 1.17 2 2.1 Example 3.18 Example 1.18 2 2.0 Example 3.19 Example 1.19 2 2.4 Example 3.20 Example 1.20 2 1.9 Example 3.21 Example 1.2 0.3 1.0 Example 3.22 Example 1. 2 1 2.2 Example 3.23 Example 1.2 20 1.7 Example 3.24 Example 1.2 35 1.0 Comparative Example 3.1 None 0 0.2 Comparative Example 3.2 Comparative Example 2.1 2 0.3 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−

[0041]

According to the present invention, a polyolefin and a polyurethane are chemically bonded to each other to form a polyurethane composite resin, whereby a high adhesion to the polyolefin material can be achieved without using a chlorinated product or an unsaturated carboxylic acid-modified polyolefin as in the prior art.
It has become possible to provide a material that achieves an adhesion improving effect.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB04 AK03B AK07 AK51A AK51G BA02 BA16 CA16G CB05 EJ38 JK06 JL11 4J034 CB01 CB03 CB04 CB05 CC03 CC08 CC23 CC37 DG03 DG04 DH04 HA07 HC03 HC12 HC13 HC17 HC18 HC73 RA05 RA08 4J040 BA202 CA002 DF042 ED002 EF002 EF051 EF071 EF111 EF131 EF181 EF251 KA26 LA06 MA11

Claims (4)

[Claims] A polyurethane composite resin obtained by reacting a monool (a) containing a hydrocarbon having 25 to 200 carbon atoms, a polyfunctional isocyanate compound (b), and an alcohol (c) other than (a). 2. A film forming material for polyolefin, comprising the polyurethane composite resin according to claim 1. 3. An adhesive for polyolefin comprising the polyurethane composite resin according to claim 1 and a tackifier. 4. A laminate obtained by laminating the polyurethane composite resin according to claim 1 on a polyolefin.