WO2014188865A1

WO2014188865A1 - Method for manufacturing polyurethane adhesive sheet and thermally dissociative bond-containing polyurethane

Info

Publication number: WO2014188865A1
Application number: PCT/JP2014/062142
Authority: WO
Inventors: 朝田　和孝; 啓司山下
Original assignee: ニチバン株式会社
Priority date: 2013-05-24
Filing date: 2014-05-02
Publication date: 2014-11-27
Also published as: JP6360046B2; JPWO2014188865A1

Abstract

The objective of the present invention is to provide a method for manufacturing a thermally processed adhesive with a new mechanism not based on reversible heating and melting of a cohesive domain, and to thereby provide an adhesive with excellent heat resistance, solvent resistance, etc. which have been issues in conventional thermal melting processed adhesives. In other words, the present invention relates to a method for manufacturing a polyurethane adhesive sheet by mixing a polyurethane (A) that includes one or more types of a thermally dissociative bond selected from an uretdione bond, biuret bond or allophanate bond and a compound (B) that includes a functional group that reacts with an isocyanate group, at a temperature equal to or higher than the temperature at which the thermally dissociative bond is able to dissociate so as to generate an isocyanate group, and forming the same into a sheet. The present invention also relates to the polyurethane (A) that includes one or more types of the thermally dissociative bond and adhesive manufacturing applications thereof.

Description

Method for producing polyurethane-based pressure-sensitive adhesive sheet and polyurethane containing thermal dissociation bond

The present invention relates to a method for producing a heat-processable polyurethane pressure-sensitive adhesive sheet, a polyurethane-based pressure-sensitive adhesive sheet obtained by the production method, and a polyurethane containing a thermally dissociable bond that can be used for the production of the pressure-sensitive adhesive.

In the production of adhesives, there is a growing demand for solvent removal from the standpoints of VOC measures and safety measures during production. Manufacturing methods other than solvent-based adhesives are roughly water-based, curable (such as photocuring and thermosetting), and hot-melt processing (such as hot-melt coating, calendar coating, and T-die extrusion coating). Exists.

Patent Document 1 describes a solventless adhesive composition containing a trifunctional isocyanate compound (D) such as a biuret formed from an aliphatic diisocyanate compound. Non-Patent Document 1 describes a polyuretdione type curing agent for polyurethane powder coatings containing a uretdione bond.
However, it is not described that it can be used for the production of polyurethane pressure-sensitive adhesives.

JP 2003-321664 A

In the water-based production method described above, the use of a surfactant is indispensable, and since this surfactant moves to the surface layer of the pressure-sensitive adhesive, the water resistance is deteriorated and the adherend is contaminated. It is difficult to produce a pressure-sensitive adhesive having the desired pressure-sensitive adhesive properties. For polyurethane, in order to eliminate the adverse effects of surfactants, self-emulsifying urethane dispersions that do not use emulsifiers have been put into practical use, but no examples have been put to practical use as pressure-sensitive adhesives.
In addition, the curable production method described above requires a polymerization reaction step at the same time as coating, so the hurdles in production are high and it is difficult to obtain stable characteristics, and the residual amount of monomer is reduced. Productivity may be sacrificed to reduce.
Among the solvent-removal techniques, the hot-melt processing type is an advantageous method in terms of reduction in adhesive properties due to impurities and productivity.

The manufacturing method of the above-mentioned hot-melt processing system has been put to practical use in various elastomers such as styrene-based, olefin-based, and acrylic-based materials, but all of them are heated by melting and softening a part of the components. Increases workability. For example, in the case of a styrene type, a domain that develops cohesive force composed of a styrene component is melted by heating to reduce the viscosity of the entire system at a high temperature, thereby improving thermal workability. In the case of acrylic, for example, methyl methacrylate-butyl acrylate-methyl methacrylate, a domain that develops cohesive force composed of methyl methacrylate is melted by heating, reducing the viscosity of the entire system at high temperature, Increases workability. In the case of an olefin type, a hard segment made of polypropylene or the like that develops a cohesive force is melted by heating to reduce the viscosity of the entire system at a high temperature, thereby improving the heat processability.
However, in these methods, since the melting and vitrification of domains are both reversible phenomena, the final product is inferior in heat resistance. In addition, the molecular weight of the elastomer is set to be relatively low in consideration of the melt viscosity, and the tackifier resin that is an oligomer component is included as an essential component, and an oil component is also included to improve processability. Since it is often contained, the solvent resistance and weather resistance are not good, and a defect derived from the contained low molecular weight component may occur.

In the case of polyurethane, as in the case of styrene-based materials, materials classified as heat-processable thermoplastic elastomers based on intermolecular interactions have been put into practical use, but as with other thermoplastic elastomers In addition, since it does not function as a pressure-sensitive adhesive alone and there is no compatible tackifier resin, a urethane-based heat-processable pressure-sensitive adhesive cannot be made from these blends. Even if it can be made, the heat-processable pressure-sensitive adhesive based on melting of the cohesive force domain has a problem that the obtained pressure-sensitive adhesive is inferior in heat resistance for the same reason as described above.

An object of the present invention is to provide a method for producing a heat-processable pressure-sensitive adhesive having a new mechanism that does not depend on reversible heat-melting of cohesive force domains, thereby causing a problem with conventional heat-melt-processable pressure-sensitive adhesives. It is to provide an adhesive having excellent heat resistance and solvent resistance.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and have completed the present invention.
That is, the present invention
Polyurethane (A) containing one or more thermally dissociable bonds selected from uretdione bonds, biuret bonds, or allophanate bonds;
A polyurethane-based pressure-sensitive adhesive characterized by mixing a compound (B) containing a functional group that reacts with an isocyanate group at a temperature at which the heat dissociable bond is dissociated to form an isocyanate group, and forming a sheet. The present invention relates to a sheet manufacturing method.
The present invention also relates to a polyurethane (A) containing one or more of the above-mentioned heat dissociable bonds and its pressure-sensitive adhesive production application.

In the present invention, one or more thermally dissociable bonds selected from a uretdione bond, a biuret bond, or an allophanate bond are introduced into the polyurethane (A). These thermally dissociable bonds are dissociated by heat to generate isocyanate groups. Therefore, the polyurethane (A) is cleaved at a heat dissociable bond by heating, and its molecular weight is lowered. Therefore, in the production of the present invention, the viscosity of the mixture of the polyurethane (A) and the compound (B) is reduced by heating, and the effect of improving the thermal processability is obtained. Moreover, since the dissociation of the thermally dissociative bond due to heat is irreversible, there is an advantage that even if the temperature of the above mixture is subsequently lowered, the workability is not lowered. After the processing is completed, the isocyanate group generated by dissociation reacts with the compound (B), a new covalent bond is generated, and an adhesive is generated.

According to the production method of the present invention, it is possible to produce a urethane-based pressure-sensitive adhesive sheet having a desired adhesive property and heat resistance while being solvent-free and hot-melt processed.
In addition, the two-component curable urethane pressure-sensitive adhesive obtained from the urethane bond of polyisocyanate and polyol that does not contain a heat dissociative bond, which is a conventional technique, is applied in a thin layer on a sheet such as release paper after mixing the two components. However, it is generally difficult to control the reactivity, and it is difficult to provide a layer with a uniform thickness and a smooth surface. However, the production method of the present invention does not have such a problem. A uniform and smooth pressure-sensitive adhesive layer can be provided with a solvent.
Furthermore, in the case of production of a two-component curable urethane pressure-sensitive adhesive, a certain degree of curing is required between coating and winding, so the production equipment includes a liquid control system that maintains low moisture, coating There is a need for a head and a long heating furnace free of moisture. On the other hand, in the manufacturing method of the present invention, since the basic structure of the manufacturing apparatus can be completed only by the heating and mixing unit and the coating head, the equipment load is small and an efficient production system can be constructed.
Moreover, in the production method of the present invention, it is possible to adjust the pressure-sensitive adhesive properties of the obtained pressure-sensitive adhesive only by changing the compound (B) that reacts with the isocyanate group without changing the polyurethane (A) of the present invention. It becomes. Thereby, in this invention, a polyurethane (A) can be manufactured with a mass production and it can respond to multi-product small-quantity production by changing a compound (B) suitably.
Furthermore, in the production method of the present invention, it is possible to obtain a molded product having adhesiveness. Even if it has a complicated shape and is made of a mold, it is possible to obtain a molded product having adhesiveness.

The polyurethane (A) of the present invention has a highly active isocyanate group protected by a heat-dissociative bond compared to ordinary polyisocyanate, and therefore suppresses reaction with moisture in the air during storage or processing. And is excellent in storage stability. As described above, the polyurethane (A) of the present invention is protected by moisture-sensitive isocyanate groups, so there is little need to strictly manage and store it in a low moisture state. Is also possible.
Further, since the polyurethane (A) of the present invention is also a solid, it is only necessary to weigh and charge the preparation, and a highly flow-controlled apparatus or the like is not necessary.
Furthermore, since the polyurethane (A) of the present invention can adjust the viscosity at the time of processing depending on the structure and average molecular weight, the coating method and head of the production apparatus can be freely selected.

It is a figure which shows the infrared absorption spectrum of the heat dissociable bond containing polyurethane obtained by making A1 and B3 react. It is a figure which shows the infrared absorption spectrum after heating the heat dissociative bond containing polyurethane obtained by making A1 and B3 react at 160 degreeC. It is a figure which shows the infrared absorption spectrum of the adhesive sheet | seat obtained by heating the heat dissociative bond containing polyurethane obtained by making A1 and B3 react at 160 degreeC, and making it react with B1 further. It is a figure which shows the infrared absorption spectrum of the heat dissociable bond containing polyurethane obtained by making A4 and B3 react. It is a figure which shows the infrared absorption spectrum of the adhesive sheet obtained by making the thermally dissociable bond containing polyurethane obtained by making A4 and B3 react, and also making it react with B4. 1 is a diagram showing a dynamic viscoelasticity chart of Example 1. FIG. It is a figure which shows the dynamic viscoelasticity chart of the adhesive [SIS (Clayton 1107) / aliphatic petroleum resin (Picotac 95) / oil = 60/50/5] which made the main raw material the styrene-type thermoplastic elastomer. : Keisuke Kurachi, "Recent tackifying resin", Adhesion, Vol. 34, No. 6, pp. 36-43, 1990).

In the present invention, polyurethane (A), or polyisocyanate or urethane prepolymer (A ′)
Uretodione binding:

Biuret coupling:

Allophanate binding:

1 type or 2 types or more of the heat dissociative bond chosen from these is included.
At least a part of the heat dissociable bond needs to be present in a portion other than the terminal in the polyurethane so that the molecular weight of the polyurethane (A) is lowered by dissociation by heating.
As the above-mentioned heat dissociable bond, an uretdione bond and an allophanate bond are preferable, and an uretdione bond is more preferable because the temperature at which an isocyanate group is generated is relatively low.

The polyurethane (A) is not particularly limited as long as it contains one or more kinds of the heat dissociable bonds, and all those that can be generally used in the field of polyurethane can be used. Specifically, a polyisocyanate or urethane prepolymer (A ′) containing one or more types of the heat dissociable bond and a compound (B ′) containing a functional group that reacts with an isocyanate group are used in a conventional method. Polyurethane obtained by reacting with a.
However, in the above reaction, the heat dissociable bond contained in the polyisocyanate or urethane prepolymer (A ′) is dissociated to obtain an isocyanate group so that the polyurethane (A) containing the heat dissociable bond is obtained. It is preferable to react at a temperature lower than the temperature at which it cannot be produced.
The polyisocyanate or urethane prepolymer (A ′) is preferably used in an amount equivalent to the compound (B ′) containing a functional group that reacts with the isocyanate group. For the purpose of controlling the adhesive properties, it is preferably used in the range of 0.5 equivalents to 1.2 equivalents.

The polyurethane (A) may or may not have tackiness, but if it does not have tackiness, it is possible to create a pellet-like raw material instead of a bale or block. For this reason, it is preferable that the material does not have tackiness because handling becomes easy in operations such as transportation, storage, and blending.
The polyurethane (A) having adhesiveness is determined by a method of evaluating known blocking in addition to the presence / absence of adhesiveness when touched with a finger (finger tack) and probe tack. In particular, the method using finger tack is preferable because it is simple.

The polyisocyanate (A ′) is not particularly limited as long as it contains one or more types of the heat dissociable bond, and the heat dissociable bond can be obtained by a known method using polyisocyanate as a raw material. It can manufacture by making it react so that it may form. As the polyisocyanate used as a raw material, generally any polyisocyanate that can be used in the production of polyurethane can be used. Specifically, toluene diisocyanate (for example, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate), 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, etc. Aromatic diisocyanates or derivatives obtained by reacting these, or aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (for example, 1,6-hexane diisocyanate), lysine diisocyanate, or obtained by reacting these. Derivatives or alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate or the like, or obtained by reaction thereof Derivatives, more organic diisocyanates or derivatives obtained by reacting these etc. These mixtures preferred. In addition, the said derivative | guide_body may contain the said thermally dissociable bond 1 type, or 2 or more types.
In addition, for the purpose of controlling thermal processability or adhesive properties, a polyisocyanate used as a raw material as described above, which does not contain a heat dissociable bond, is optionally used as a polyisocyanate of (A ′). You may use together. The amount is preferably 0 to 0.75 equivalents relative to the compound (B ′) from the viewpoint of thermal processability. When the amount of polyisocyanate that does not contain such a thermal dissociation bond is increased, the portion that undergoes thermal dissociation during processing decreases, so that the viscosity during processing tends to increase. It is possible to control the viscosity at the time of processing by the ratio of the thermally dissociative bond and the bond that does not dissociate.
The polyisocyanate of (A ′) or a derivative containing one or more of the above heat dissociable bonds, specifically, a commercially available product, which is a toluene diisocyanate dimer (uretdione form): AddlinkTT (Rhein Chemie), a mixture containing uretdione of hexamethylene diisocyanate, Desmodur N3400, Desmodur XP-2840, Desmodur XP-2730 (Bayer Material Science), allophanate of hexamethylene diisocyanate Desmodur XP-2580, Desmodur XP-2714 (Bayer Material Science), Takenate D-178N (Mitsui Chemicals), a mixture containing hexamethylene diisocyanate biuret, Desmodur N100, Desmodur N3200 ( Bayer Material Science), Duranate 24A-100 (Asahi Kasei Chemicals), Takenate D-165N (Mitsui Chemicals), allophane of isophorone diisocyanate And the like is a mixture containing a preparative body Desmodur XP2565.
From the viewpoint of the decomposition temperature, hexamethylene diisocyanate (eg 1,6-hexane diisocyanate) dimer (uretdione) and toluene diisocyanate (eg 2,4-toluene diisocyanate) dimer (uretdione) Or a polyisocyanate containing a dimer (uretdione form) of isophorone diisocyanate.

In the present invention, the compounds (B) and (B ′) containing a functional group that reacts with an isocyanate group may be the same or different, and are not particularly limited as long as they contain a functional group that reacts with an isocyanate group. Anything that can be used to produce a polyurethane resin can be used.
Examples of the functional group that reacts with the isocyanate group include active hydrogen groups such as a hydroxyl group, an amino group, and a carboxyl group, and the active hydrogen group is particularly preferably a hydroxyl group.
The compound (B) may contain at least one functional group that reacts with an isocyanate group in one molecule, preferably from the viewpoint of improving the heat resistance and solvent resistance of the resulting pressure-sensitive adhesive sheet. 2 or more, more preferably at least 2 at both ends.
On the other hand, the compound (B ′) needs to contain two or more functional groups that react with isocyanate groups in one molecule, and preferably contains at least two functional groups at both ends.

Preferably, the compounds (B) and (B ′) include active hydrogen group-containing compounds containing an active hydrogen group as a functional group that reacts with an isocyanate group. Examples of such active hydrogen group-containing compounds include polyhydric alcohols, particularly saturated polyhydric alcohols.
The polyhydric alcohol has, for example, 2 to 20, preferably 2 to 9, more preferably 4 to 8 carbon atoms. The polyhydric alcohol may contain hydroxyl groups at least at both ends. Specifically, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,12-dodecanediol. Is exemplified. In addition, the high molecular weight thing is preferable from the point which the adhesiveness of the adhesive sheet obtained is improved, and especially the polymer illustrated below is preferable for the said compound (B ').

Alternatively, as the active hydrogen group-containing compound, particularly the compound (B ′), a polyester polyol, a polycarbonate diol, a polyether polyol, an ether ester polyol in which a polyether polyol is partially ester-modified, a hydroxyl group-terminated polybutadiene, a hydroxyl group-terminated polyisoprene, Examples thereof include vegetable oil-based polyols and polyalkylenes having amino groups (such as ethylene and propylene) and oxide diamines, and polyester polyols are preferred from the viewpoints of heat resistance, cost, and supply.

As the polyester polyol, any of those generally usable for the production of polyurethane pressure-sensitive adhesives can be used, specifically, those produced by polycondensation of a polyvalent carboxylic acid and the polyhydric alcohol, or Examples thereof include ring-opening polymerization of ε-caprolactone.
The polyvalent carboxylic acid preferably has 4 to 8 carbon atoms. Specifically, examples of the polyvalent carboxylic acid include polyvalent carboxylic acids containing carboxyl groups at least at both ends, and more specifically, adipic acid, terephthalic acid, isophthalic acid, and sebacic acid.
Specifically, DIC's Polylite series, Kuraray's Kuraray polyol P series, F series, Ube Industries' Etanacol 3000 series, Toyokuni Oil Polyester polyol products, Daicel's Plaxel 200 series, 300 series, Nippon Polyurethane Industrial Nipponran etc. can be used. The polyester polyol is obtained by polycondensing at least a polyhydric carboxylic acid having 4 to 8 carbon atoms containing carboxyl groups at both ends and a polyhydric alcohol having 2 to 9 carbon atoms containing hydroxyl groups at both ends. In particular, those obtained by polycondensation of a polyvalent carboxylic acid and a diol containing a branched structure are preferable because a pressure-sensitive adhesive sheet having a flexible structure can be obtained by the diol containing a branched structure.

Examples of the polycarbonate diol include polycarbonate diols obtained by copolymerization of the polyhydric alcohol, for example, 1,6-hexanediol with other diols, or copolymerization with a polyester such as caprolactone. Specifically, Ube Industries' Etanacol UH, UHC, UC, UM series, Daicel's Plaxel CD series, Kuraray's Kuraray polyol C series, Asahi Kasei Chemical's Duranol series, etc. can be used. As the polycarbonate diol, a pressure-sensitive adhesive sheet having a flexible structure can be obtained by copolymerization with a diol containing a branched structure or copolymerization with polyester.

As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or the like, having an average number of functional groups of 2, was copolymerized. A polyether glycol such as polyether glycol, or a mixture of two or more polyols having these two average functional groups is preferred.
Moreover, as said polyether polyol, for example, those having an average functional group number of 3 or more, those having 3 or more active hydrogen groups such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose as an initiator, ethylene oxide, Polyether polyols obtained by ring-opening polymerization of propylene oxide, tetrahydrofuran, etc., polyether polyols such as polypropylene polyols and polytetramethylene ether polyols, or a mixture of two or more polyols having an average functional group number of 2 or 3 are preferred. .
Specifically, Sanyo Chemical's Sanniks series, Mitsui Chemicals Polyurethane's Act Call series, Asahi Denka's Adeka polyether series, Lyondell's Acclaim series, Asahi Glass's Exenol series, Preminol series, etc. Can be used.
In the present invention, each of the active hydrogen compounds can be used alone, but for example, a mixture of two or more kinds different in average molecular weight, average number of functional groups, types of monomer units, and the like may be used.

The average molecular weights of the compounds (B) and (B ′) are not particularly limited, but (B ′) is 5 × 10 ² or more, preferably 1 × 10 ³ or more, from the viewpoint of the flexibility of the product. Preferably, it is 2 × 10 ³ or more, and the upper limit is not particularly limited, but for example, 2 × 10 ⁴ or less can be used from the viewpoint of obtaining raw materials.
In the present invention, the average molecular weight is expressed by the following formula based on the hydroxyl value (OHv, unit is mgKOH / g):
Average molecular weight = (56100 / OHv) × Calculated using the average number of hydroxyl groups per molecule. Here, the hydroxyl value is a value measured according to JIS K1557-1 (2007 edition) B method (phthalation method). The average number of hydroxyl groups per molecule refers to the number of active hydrogen atoms per molecule of initiator used as a raw material when producing an active hydrogen compound. For example, ethylene glycol and propylene glycol are 2, Glycerin and trimethylolpropane are three. Similarly, the average molecular weight when the active hydrogen group is other than a hydroxyl group can also be calculated. For example, it can be calculated from the amine value when the active hydrogen group is an amino group, and from the acid value when the active hydrogen group is a carboxyl group. Here, the amine value and the acid value are values measured in accordance with JIS K-7237 or JIS K-1557-5, respectively.

A compound containing a functional group that reacts with an isocyanate group other than the compounds (B) and (B ′) may be used for producing the polyurethane pressure-sensitive adhesive of the present invention. For example, other active hydrogen compounds such as monools and polyols can be used as long as the effects of the present invention are not impaired. As such active hydrogen compounds such as monools and polyols, general compounds such as acrylic monools, ester polyols, and polycarbonate polyols can be used.

The urethane prepolymer (A ′) is not particularly limited as long as it contains one or more types of the heat dissociable bond, and the polyisocyanate and the compound (B ′) are combined with an active hydrogen as an isocyanate group. By reacting so that the thermally dissociable bond is formed by a known method under a condition in which the group exists in excess of the group (for example, an isocyanate group is 1.5 to 2.0 equivalents relative to the active hydrogen group). Can also be manufactured. As the polyisocyanate, any of those generally usable for the production of polyurethane can be used, and not only the polyisocyanate used as a raw material for the polyisocyanate of (A ′), but also the polyisocyanate of (A ′) itself. Can also be used.
Preferably, the urethane prepolymer (A ′) is, for example, an aliphatic or aromatic polyisocyanate containing a heat dissociable bond and an average molecular weight of 5 × 10 ² to 2 × 10 ⁴ . In addition, a urethane prepolymer obtained by reacting an active hydrogen group-containing compound containing two or more active hydrogen groups in one molecule under a condition in which an isocyanate group is present in excess of the active hydrogen group is exemplified.
However, the above reaction cannot generate an isocyanate group by dissociating the thermally dissociable bond contained in the polyisocyanate so that the urethane prepolymer (A ′) containing the thermally dissociable bond is obtained. It is preferable to make it react below temperature.

In the present invention, the polyurethane (A) and the compound (B) are mixed at a temperature equal to or higher than a temperature at which the thermally dissociable bond dissociates to form an isocyanate group (hereinafter also referred to as “thermal dissociation temperature”). A polyurethane-based pressure-sensitive adhesive sheet is produced by coating the material by a known method. In the present invention, a reaction such as dissociation of the thermal dissociation bond or formation of a polyurethane bond proceeds from the mixing to the sheet formation, and a polyurethane-based pressure-sensitive adhesive layer is formed.
The dissociation of the thermally dissociative bond can be detected by an infrared spectrophotometer. In the present invention, it is sufficient that the thermally dissociable bond is dissociated to generate an isocyanate group to such an extent that the heat processability of the mixture of the polyurethane (A) and the compound (B) can be improved. The thermal dissociation temperature can be appropriately set according to the type of thermal dissociable bond, the number of polyurethane (A) in one molecule, and the like. For example, for uretdione bonds, 100 ° C or higher, preferably 120 ° C or higher, more preferably 140 ° C or higher; for biuret bonds, 160 ° C or higher, preferably 180 ° C or higher; for allophanate bonds, 140 ° C or higher, preferably 160 ° C or higher. is there.
The upper limit of the thermal dissociation temperature is preferably 200 ° C. or less, particularly 190 ° C. or less, particularly 180 ° C. or less, from the viewpoint of heat resistance of the polyurethane.

The processing (mixing, coating) time is not particularly limited as long as the heat dissociable bond can be dissociated to generate an isocyanate group, and the heat dissociation temperature, the type of heat dissociable bond, polyurethane (A ) It can be appropriately set according to the number in one molecule, the device, and the like. For example, it is about 10 minutes to 120 minutes.

In the production of the polyurethane pressure-sensitive adhesive sheet of the present invention, when the polyurethane (A) is 100 parts by mass from the viewpoint of balance between processability, adhesive force and cohesive force, the compound (B) is, for example, 1 to 150 parts by mass, preferably 1 to 100 parts by mass, more preferably 1.5 to 100 parts by mass, and particularly preferably 2 to 75 parts by mass are added.

The NCO / OH molar ratio between the isocyanate that appears by thermal dissociation in the polyurethane (A) and the compound (B) is preferably 1/1 to increase the polymer molecular weight, but is preferably 0.1 to control the characteristics. It may be changed in the range of 5/1 to 1.2 / 1.

In the production of the polyurethane pressure-sensitive adhesive sheet in the present invention, first, a polyurethane (A) containing a thermally dissociable bond is produced, and this polyurethane (A) and a compound (B) containing a functional group that reacts with an isocyanate group are produced. And a step of mixing in a heated state, forming a sheet by coating on a substrate or a release sheet, and obtaining an adhesive sheet. Moreover, the method of forming into a sheet by the co-extrusion system which forms an adhesive layer simultaneously at the time of film forming can also be employ | adopted.
For the production of the polyurethane (A), for example, a usual method such as a bulk polymerization method or a solution polymerization method can be used. Specific examples of the solvent used in the solution polymerization method include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and tetrahydrofuran, There are glycol ether solvents such as cellosolve and carbitol, glycol ether solvents such as cellosolve acetate, amide solvents such as dimethylacetamide and dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and mixed solvents thereof. Can be mentioned.
Preferably, it is a substantially solvent-free production method that does not use a solvent, such as a bulk polymerization method. Since a solvent is not used, a process for removing the solvent or preparing a raw material solution is not necessary, so that the polyurethane pressure-sensitive adhesive sheet of the present invention can be easily produced and has excellent environmental measures. ing. When the polyurethane (A) is produced by this method, the compound (B ′) containing a functional group that reacts with an isocyanate group is in a liquid state at room temperature, and is used for producing the polyurethane (A). When the polyisocyanate is liquid or dissolved in the compound (B ′), since heating is not necessary, the polyurethane (A) can be produced only by mixing with a stirrer.
The pressure-sensitive adhesive sheet of the present invention can be obtained by mixing the polyurethane (A) and the compound (B) thus obtained in a heated state and coating them in a sheet form.
The substantially solvent-free production method refers to a production method in which the concentration of residual solvent contained in the final product is less than 5 ppm, more preferably less than 1 ppm.

When producing the polyurethane pressure-sensitive adhesive sheet in the present invention, a catalyst, an additive and the like can be used as necessary. Examples of the catalyst include general urethanization catalysts such as nitrogen-containing compounds and organometallic catalysts. Examples of nitrogen-containing compounds include triethylamine and triethylenediamine. Examples of organometallic catalysts include dialkyltin compounds {eg, dibutyltin dilaurate, dibutyltin di (2-ethylhexoate)}, carboxylic acid metal catalysts (eg, octylic acid). Tin, tin stearate) and the like. By using a catalyst, it becomes possible to increase the reaction rate when producing the polyurethane (A), or to change the dissociation temperature of the thermally dissociative bond contained in the polyurethane (A). Examples of the additive include ultraviolet absorbers such as substituted benzotriazoles, antioxidants such as phenol derivatives, and hydrolysis inhibitors.

Further, in order to improve cohesive strength, a compound having a trifunctional or higher functional group such as 3-methyl-1,5-penta-diol, trimethylolpropane, and adipic acid is used in combination with the compound (B). You may add the polyester polyol obtained by making these react.

In the present invention, the number of the thermal dissociation bonds, and the types and blending ratios of the polyurethane (A) and the compound (B) can be freely changed, and thereby the adhesive properties of the resulting adhesive sheet can be changed. It can be adjusted easily. If there is an existing solvent-type polyurethane-based pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet of the present invention can be designed using that as a model.

According to the production method of the present invention, the concentration of the residual solvent in the polyurethane pressure-sensitive adhesive is less than 5 ppm, preferably less than 1 ppm, and the flat region of G ′ is −20 to 170 ° C., preferably 0 to 150 ° C. An adhesive sheet containing a polyurethane-based adhesive can be obtained. The present invention also relates to such an adhesive sheet.

The present invention also relates to the polyurethane (A). In particular, the present invention is a polyurethane (A) obtained by reacting the polyisocyanate or urethane prepolymer (A ′) with the active hydrogen group-containing compound; the active hydrogen group-containing compound is a polyester. The present invention also relates to a polyurethane (A) containing any one of a polyol, a polycarbonate diol, a polyether polyol, and a hydroxyl group-terminated polybutadiene and having an average molecular weight of 5 × 10 ² or more of the active hydrogen group-containing compound.

The present invention also relates to an adhesive production application of the polyurethane (A).
That is, the present invention relates to the use of the polyurethane (A) or the polyisocyanate or urethane prepolymer (A ′) and the compound (B) for the production of a polyurethane-based pressure-sensitive adhesive, particularly for the production of the present invention. Also related to the use of ').

The present invention further includes a composition for producing a polyurethane-based pressure-sensitive adhesive, particularly the present composition, containing the polyurethane (A), or containing the polyisocyanate or urethane prepolymer (A ′) and the compound (B ′). It also relates to the composition for manufacture of the invention.
In addition to the polyurethane (A), the polyisocyanate or urethane prepolymer (A ′), and the compound (B ′), the polyurethane pressure-sensitive adhesive production composition includes any component, for example, the present invention. The catalyst or additive used in the production of the polyurethane pressure-sensitive adhesive sheet can be included.

According to the production method of the present invention, a pressure-sensitive adhesive sheet containing a polyurethane-based pressure-sensitive adhesive substantially free from a tackifier resin and an oil component and having a residual solvent in the polyurethane-based pressure-sensitive adhesive of less than 5 ppm, preferably less than 1 ppm. Can be obtained. The present invention also relates to such an adhesive sheet.

As the tackifier resin and the oil component, those that can be generally used for the production of the pressure-sensitive adhesive can be used. Specifically, as the tackifier resin, a natural resin composed of a rosin resin, a terpene resin, or the like. In addition to these systems, petroleum resin systems, and synthetic resin systems composed of other resins including alkylphenol resins and chroman indene resins are exemplified, and oil systems such as process oil and extender oil, liquid polyisobutylene, liquid polybutene, liquid Examples include liquid rubbers such as polyisoprene and synthetic plasticizers such as dibasic acid esters. In addition, the above “substantially free” means an amount such that the tackifier resin and the oil component cannot exert the function / effect of the purpose of addition. It is 1 mass% or less about an oil component, More preferably, it is 0.1 mass% or less, More preferably, it is 0.1 mass% or less.

The mixture of the polyurethane (A) and the compound (B) used in the production of the pressure-sensitive adhesive sheet of the present invention is not particularly limited in melt viscosity at 160 ° C., but preferably 1 × 10 ⁴ to 1 ×. It is in the range of 10 ⁷ centipoise, more preferably 1 × 10 ⁴ to 1 × 10 ⁶ centipoise. A range of 1 × 10 ⁴ to 1 × 10 ⁶ centipoise is convenient for hot melt coating, and a range of 1 × 10 ⁵ to 1 × 10 ⁷ centipoise is convenient for calendar coating. Furthermore, even when the viscosity is high, coating can be performed by using an extruder. The melt viscosity is usually the number of thermal dissociation bonds in the polyurethane (A), the molecular weight of the compound (B ′) or the average number of functional groups, or the number of functional groups of the polyisocyanate or urethane prepolymer (A ′). Can be adjusted.

The polyurethane-based pressure-sensitive adhesive of the pressure-sensitive adhesive sheet of the present invention preferably has a storage elastic modulus of 10 ⁷ dyn / cm ² or less at room temperature (25 ° C.) in order to exhibit a good pressure-sensitive adhesive function. The lower limit of the storage elastic modulus is not particularly limited, but 10 ⁴ dyn / cm ² is exemplified. The storage elastic modulus can be usually adjusted by controlling the structure and average molecular weight of the active hydrogen compound, the structure and average molecular weight of the polyisocyanate, or the NCO / OH ratio.

The polyurethane pressure-sensitive adhesive of the pressure-sensitive adhesive sheet of the present invention preferably has a glass transition point of 0 ° C. or lower, more preferably −20 ° C. or lower in order to exhibit a good pressure-sensitive adhesive function. The lower limit of the glass transition point is not particularly limited, but is exemplified by −60 ° C. The glass transition point can usually be adjusted by controlling the structure and average molecular weight of the active hydrogen compound, the structure and average molecular weight of the polyisocyanate, or the NCO / OH ratio.

It should be understood that the pressure-sensitive adhesive sheet of the present invention can include not only a sheet shape but also a film shape, a wrap shape, a plate shape, a strip shape, a tape shape and the like.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following examples and comparative examples, parts and% indicate, in principle, parts by mass and mass%, respectively.

1. Raw materials The raw materials used below and their amounts used are shown in Tables 1 and 2. The amount used is expressed in parts. The raw materials shown in Tables 1 and 2 are as follows.
A1: HDI polyisocyanate, containing uretdione, manufactured by Bayer Material Science, trade name Desmodur N-3400;
A2: HDI polyisocyanate, containing biuret, manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate 24A-100;
A3: HDI polyisocyanate, containing allophanate, manufactured by Mitsui Chemicals, Inc., trade name Takenate D-178L;
A4: TDI polyisocyanate, containing uretdione, manufactured by Rhein Chemie, trade name addlinkTT;
A5: HDI polyisocyanate, isocyanurate body, Bayer Material Science_, trade name Desmodur N-3300;
A6: hexamethylene diisocyanate;
B1: 1,6-hexanediol B2: 1,12-dodecanediol B3: Polyester polyol obtained by reacting 3-methyl-1,5-pentadiol with adipic acid, average molecular weight: 6000, Kuraray Co., Ltd. Product name Kuraray Polyol P-6010;
B4: Polyester polyol obtained by reacting 3-methyl-1,5-penta-diol with adipic acid, average molecular weight: 2000, manufactured by Kuraray Co., Ltd., trade name Kuraray Polyol P-2010;
B5: polyester polyol obtained by reacting 3-methyl-1,5-penta-diol with terephthalic acid, average molecular weight: 2000, manufactured by Kuraray Co., Ltd., trade name Kuraray Polyol P-2020;
B6: polyester polyol obtained by reacting iND and adipic acid, average molecular weight: 5000, manufactured by Toyokuni Oil Co., Ltd., trade name HS2N-521A;
B7: Polyester polyol obtained by reacting propylene glycol and sebacic acid, average molecular weight: 8000, manufactured by Toyokuni Oil Co., Ltd., trade name HSPP-830S;
B8: Polycarbonate diol obtained by reacting 1,6-hexanediol and caprolactone, average molecular weight: 2000, manufactured by Ube Industries, Ltd., trade name ETERNACOLL UHC50-200:
B9: Polyether polyol obtained by reacting tetrahydrofuran and neopentyl glycol, average molecular weight: 1860, manufactured by Asahi Kasei Fibers Co., Ltd., trade name PTXG;
B10: Hydroxyl-terminated polybutadiene, average molecular weight: 3000, manufactured by Cray Valley, trade name KRASOL LBH-3000;
B11: polyester polyol obtained by reacting 3-methyl-1,5-penta-diol, trimethylolpropane, and adipic acid, average molecular weight: 3000, manufactured by Kuraray Co., Ltd., trade name Kuraray polyol F-3010;

2. Preparation of heat-dissociative bond-containing polyurethane The isocyanate (A ′) and optionally added A6 shown in Tables 1 to 3 and the compound (B ′) were converted to an NCO / OH molar ratio of 1.0 / 1.0. As described above, a heat dissociable bond-containing polyurethane (A) was prepared by stirring and mixing with a stirrer and heating the mixture at 60 ° C. The reaction was terminated when the isocyanate absorption disappeared with an infrared spectrophotometer.
In addition, the adhesiveness of the obtained polyurethane (A) was determined by the method described in the literature (Japan Adhesive Tape Industry Association, Adhesive Handbook Editorial Committee, “Adhesive Handbook 3rd Edition”, page 243, issued on October 1, 2005). , Sensory evaluation of the thumb of the polyurethane (A) against the thumb that was momentarily applied to the polyurethane (A) (finger tack method; ◎: no tack on the finger, ○: very small tack feeling △: There is a minute tack, ×: There is an obvious tack). The results are shown in Tables 1-3.

3. Preparation of polyurethane-based pressure-sensitive adhesive sheet Compound (B) was mixed with 100 parts by mass of the heat-dissociable bond-containing polyurethane (A) obtained above, as shown in Tables 1 to 3, to obtain a polyurethane-based pressure-sensitive adhesive. Prepared and sheeted on release paper with a hot press, laminated a PET film (thickness 25 μm), and aged at 23 ° C. for 5 days or longer to produce Examples 1 to 17. On the other hand, since Comparative Example 1 does not cause softening even when heated and stirred, a uniform compound cannot be obtained, and a sheet-like molded product cannot be obtained even by hot pressing. Could not be produced.
The polyurethane (A) was added so that the isocyanate group generated when the thermally dissociative bond was dissociated 100% had a ratio of 1 equivalent to the hydroxyl group of the compound (B).
However, for A1, A2, and A3, the amount of the thermally dissociable bond is an estimated value.

Comparative Example 2
According to the following procedure, production of a two-component curable urethane pressure-sensitive adhesive sheet was also attempted.
First, A6 and propylene glycol (Mw: 2000) are uniformly mixed with a two-liquid mixing pump so that the equivalent becomes 1/1, and the mixed liquid is put into a knife coater to prepare the above-mentioned pressure-sensitive adhesive sheet. Similarly, coating was performed on the release paper so as to have a thickness of 300 μm, but the repelling of the coating solution partially occurred on the release paper. Even if the mixing speed was adjusted, it was difficult to manage the viscosity, and a uniform coating layer could not be obtained.

4). Evaluation of thermal processability Qualitative evaluation was made on processability in the preparation of the above-mentioned pressure-sensitive adhesive sheet (◎: liquefied by heat at 160 ° C, can be formed into a good sheet, ○: although not liquefied by heat at 160 ° C , Can be made into a good sheet, Δ: difficult to smooth the sheet, but can be made into a sheet, x cannot be made into a sheet). The results are shown in Tables 1-3.

5. Measurement of infrared absorption spectrum A1 and B3 were reacted in the same manner as in the preparation of the heat dissociable bond-containing polyurethane to obtain a heat dissociable bond-containing polyurethane. When the infrared absorption spectrum of the polyurethane was measured, absorption of uretdione bonds (1767 cm ⁻¹ ) was observed (FIG. 1). Next, when the polyurethane was heated at 160 ° C. for 30 minutes, absorption of isocyanate groups (2270 cm ⁻¹ ) was observed, while absorption of uretdione bonds (1767 cm ⁻¹ ) disappeared (FIG. 2). Further, the heated polyurethane and B1 were reacted in the same manner as in the preparation of the polyurethane-based pressure-sensitive adhesive sheet to obtain a pressure-sensitive adhesive sheet. Was measured infrared absorption spectrum of the pressure-sensitive adhesive sheet, the absorption of the absorption of isocyanate group (2270 cm ^-1) and uretdione bond (1767cm ^-1) has disappeared, the progress of the reaction was confirmed (Fig. 3) .
A4 and B3 were reacted in the same manner as in the preparation of the heat dissociable bond-containing polyurethane to obtain a heat dissociable bond-containing polyurethane. When the infrared absorption spectrum of the polyurethane was measured, there was no isocyanate group absorption (2270 cm ⁻¹ ), and uretdione bond absorption (1781 cm ⁻¹ ) was observed (FIG. 4). Next, the said polyurethane and B4 were made to react similarly to preparation of the said polyurethane-type adhesive sheet, and the adhesive sheet was obtained. Was measured infrared absorption spectrum of the pressure-sensitive adhesive sheet, the absorption of the absorption of isocyanate group (2270 cm ^-1) and uretdione bond (1781cm ^-1) has disappeared, the progress of the reaction was observed (Fig. 5) .
As described above, when the heat-dissociative bond-containing polyurethane (A) before heat processing and the infrared absorption spectrum of the pressure-sensitive adhesive sheet obtained after heat processing are compared, the peak derived from the heat-dissociative bond is caused by heat processing. Dissociated, combined with property change during heating (lower viscosity) and cohesive strength after processing, bond dissociation, and reaction between isocyanate group generated by dissociation and compound (B) was performed It is inferred.

6). Measurement of adhesive properties The adhesive properties and the like of the adhesive sheet produced above were measured by the tests shown below. The results are shown in Tables 1-3.

(1) Preparation of test piece For the adhesive sheets of Examples 1 to 17 and Comparative Example 1 obtained above, the MD direction of the base material was measured for measurement of SUS adhesive force, probe tack, and holding force. A test piece was prepared by cutting into a width of 12 mm and a length of 75 mm so as to be the long side of the sample.
(2) Adhesive strength against SUS In accordance with JIS Z-0237, a 12 mm wide test piece was affixed to a SUS304 steel plate at 23 ° C. and 50% RH, and one round trip was performed at a speed of 300 mm / min with a 2 kg rubber roll. After crimping and leaving for 20 minutes, 180 ° peeling force was measured at a peeling speed of 300 mm / min (average value of 3 specimens).
(3) Probe tack According to ASTM D-2979, using an NS probe tack tester (manufactured by Nichiban Co., Ltd.) in an atmosphere of 23 ° C. and 50% RH, a probe having a diameter of 5 mm, a pressure of 0.98 N / cm ² , The measurement was performed under the conditions of a contact time of 1 second and a peeling speed of 10 mm / sec (average value of 3 samples).
(4) Holding force According to JIS Z-0237, it was attached to a glass plate so as to have an area of 12 mm × 20 mm under an atmosphere of 23 ° C. and 50% RH, and was subjected to one reciprocal pressing with a 2 kg rubber roll at a speed of 300 mm / min. After standing for 20 minutes, the patch was hung so as to hang vertically, a load of 0.5 kg was applied, and the deviation length (mm) or drop time after 60 minutes was measured.

From Tables 1 to 3, it was confirmed that the pressure-sensitive adhesive sheet of the present invention has sufficient pressure-sensitive adhesive properties even without including a low molecular weight component such as a tackifier resin.
As is clear from a comparison between Examples 9 and 10, the degree of cross-linking can be adjusted by adding a compound (B11) having a trifunctional or higher functional group as (B). It is possible to obtain a pressure-sensitive adhesive sheet excellent in solvent resistance.
Furthermore, as shown in Table 3, even if an isocyanate compound having no thermal dissociation bond is added, a pressure-sensitive adhesive sheet having sufficient heat processability can be obtained.
In Examples 8 and 11 to 15 where the thermal processability was “◎”, hot melt coating was easy. In Examples in which the remaining heat processability was “◯” or “Δ”, hot melt coating was difficult, but calendar coating was easy.

7). Measurement of dynamic viscoelasticity The dynamic viscoelasticity of Example 1 was obtained by using an MCR-301 manufactured by Anton Paar, using a 20 mmφ parallel plate, a strain of 0.05% swing and a frequency of 1 Hz. It investigated by the temperature dispersion measurement to 200 degreeC. According to the obtained dynamic viscoelasticity chart, the flat region of G ′ extends to around 170 ° C., and a pressure-sensitive adhesive using a styrene thermoplastic elastomer as a main raw material (G ′ decreases from around 100 ° C.) It is expected that the heat resistance is high as compared with (Figs. 6 and 7).

According to the present invention, it is possible to produce a pressure-sensitive adhesive sheet that can be solvent-free and heat-processed with a new mechanism that does not depend on reversible heating and melting of cohesive force domains. The pressure-sensitive adhesive sheet of the present invention has excellent heat resistance. Furthermore, the pressure-sensitive adhesive sheet of the present invention can exhibit sufficient adhesive properties without containing a low molecular weight component such as a tackifier resin or an oil component, and the functional group having three or more functional groups as the compound (B). Since the degree of cross-linking can be adjusted by adding a compound having the above, a pressure-sensitive adhesive sheet excellent in weather resistance and solvent resistance can also be obtained.
With the method of the present invention, it is possible to apply a solvent-free adhesive to applications that required heat resistance, weather resistance, and solvent resistance, which were difficult to adapt with conventional hot-melt adhesives. Become.
Moreover, the polyurethane (A) of the present invention can be used as a raw material for producing an adhesive.

Claims

Polyurethane (A) containing one or more thermally dissociable bonds selected from uretdione bonds, biuret bonds, or allophanate bonds;
A polyurethane-based pressure-sensitive adhesive characterized by mixing a compound (B) containing a functional group that reacts with an isocyanate group at a temperature at which the heat dissociative bond is dissociated and an isocyanate group can be formed to form a sheet. Sheet manufacturing method.
The polyurethane (A) is at least
Compound (B ′) containing a polyisocyanate or urethane prepolymer (A ′) containing one or more thermally dissociable bonds selected from uretdione bonds, biuret bonds, or allophanate bonds, and a functional group that reacts with isocyanate groups The manufacturing method of Claim 1 obtained by making these react.
The production according to claim 2, wherein the compound (B ') is an active hydrogen group-containing compound having an average molecular weight of 5 x 10 2 to 2 x 10 4 and containing two or more active hydrogen groups in one molecule. Method.
The active hydrogen group-containing compound is at least
A polyvalent carboxylic acid having 4 to 8 carbon atoms containing a carboxyl group at both ends;
The production method according to claim 3, which is a polyester polyol obtained by polycondensation with a polyhydric alcohol having 2 to 9 carbon atoms containing hydroxyl groups at both ends.
The production method according to claim 4 , wherein the polyester polyol has an average molecular weight of 2 × 10 3 to 2 × 10 4 .
The production method according to claim 4 or 5, wherein the polyester polyol is obtained by polycondensation of a polycarboxylic acid and a diol containing a branched structure.
The production method according to any one of claims 1 to 6, wherein the polyurethane (A) contains an allophanate or uretdione bond.
The production method according to any one of claims 1 to 7, wherein the polyurethane (A) contains a uretdione bond.
9. The polyurethane according to claim 1, wherein 100 parts by mass of the polyurethane (A) and 1 to 150 parts by mass of the compound (B) are mixed at 120 to 190 ° C. for 10 to 120 minutes. The manufacturing method of 1 item | term.
The glass transition point of the polyurethane adhesive in the polyurethane adhesive sheet is less than 0 ° C., and the storage elastic modulus of the adhesive is from 10 4 to 10 7 dyn / cm 2. Item 10. A production method without solvent according to any one of Items 1 to 9.
A polyisocyanate or urethane prepolymer (A ′) containing one or more thermally dissociable bonds selected from a uretdione bond, a biuret bond, or an allophanate bond;
A polyurethane (A) obtained by reacting an active hydrogen group-containing compound containing two or more active hydrogen groups in one molecule,
The active hydrogen group-containing compound includes any of polyester polyol, polycarbonate diol, polyether polyol, and hydroxyl group-terminated polybutadiene, and the average molecular weight of the active hydrogen group-containing compound is 5 × 10 2 or more.
Polyurethane (A).