JP6733601B2 - Isocyanate group-containing organosilicon compound and method for producing the same - Google Patents

Description

The present invention relates to an isocyanate group-containing organosilicon compound and a method for producing the same, and more specifically, it has a plurality of isocyanate groups in one molecule, and a sulfur atom is always present in the chain connecting the isocyanate group and the hydrolyzable silyl group. The present invention relates to an isocyanate group-containing organosilicon compound and a method for producing the same.

The silane coupling agent has two or more different functional groups in the molecule, and acts as an intermediary for connecting an organic material and an inorganic material, which are usually difficult to bond. One of the functional groups is a hydrolyzable silyl group, which produces a silanol group in the presence of water, and the silanol group reacts with the hydroxyl group on the surface of the inorganic material to form a chemical bond with the surface of the inorganic material. The other functional group is an organic reactive group such as a vinyl group, an epoxy group, an amino group, a (meth)acryl group, a mercapto group, or an isocyanate group which forms a chemical bond with an organic material such as various synthetic resins. With such characteristics, it is widely used as a modifier for organic/inorganic resins, an adhesion aid, various additives and the like.

Among the silane coupling agents, those having an isocyanate group are particularly excellent in reactivity with active hydrogen-containing groups such as hydroxyl groups, primary and secondary amino groups, and carboxy groups, and therefore can be added to an adhesion improver or an organic polymer. It is useful as a resin modifier for introducing a degradable silyl group.

Several methods for efficiently and industrially producing an organosilicon compound having an isocyanate group have been proposed, and generally, a method of reacting an amine with phosgene (Patent Documents 1 to 3 or the like) or a pyrolysis of carbamate. (Patent documents 4-7) are mentioned.
The former method is difficult to handle from the viewpoint of the toxicity of phosgene, and there is still a problem in terms of productivity in capturing and removing the generated hydrochloride.
The latter method is less prevalent than the phosgene method and has less toxicity and less by-products, so it has become the mainstream for small-to-medium-scale isocyanate production, but it is necessary to introduce a production device that efficiently removes alcohol generated at high temperatures. Yes, there are challenges from an industrial point of view.

By the way, as a general method for synthesizing a silane coupling agent, a method based on a hydrosilylation reaction of hydrosilane and an olefin compound is known.
When considering applying this method to isocyanate silane, hydrosilylation with hydrosilane and a polymerizable group-containing isocyanate can be mentioned. However, this reaction is not practical because it becomes a catalyst poison for the platinum complex, which is a nitrogen-containing compound and is a catalyst for hydrosilylation reaction.

Further, by reacting 1 mol of an industrially easily available diisocyanate compound with 1 mol of an organosilicon compound having an active hydrogen-containing group such as aminosilane or mercaptosilane, an organosilicon compound in which an unreacted isocyanate group remains can be obtained. However, in this case, since there is no selectivity in the reactivity between the isocyanate and the active hydrogen-containing group, not only the case where the raw material diisocyanate remains but also the NH structure of the urea bond and the thiourethane bond generated by the reaction and the residual isocyanate However, it is difficult to obtain the target product as a single substance, and a problem remains in the stability of the obtained reaction product.

As described above, the production method of the silane coupling agent having an isocyanate group is industrially limited, and the silane coupling agent having a plurality of isocyanate groups in one molecule has a large number of reaction points with an organic resin and has a high coupling capacity. Expected to exhibit ring properties.
Aminosilane (Patent Document 8), epoxysilane (Patent Documents 9 and 10), (meth)acrylsilane (Patent Document 11) and the like are known as useful silane coupling agents developed under the same concept.
Although the silane coupling agent of Patent Document 10 has a structure having a sulfur atom in the connecting chain of the hydrolyzed silyl group and the epoxy group, it uses a strongly basic amine compound such as diazabicycloundecane during its production. Therefore, when an isocyanate structural group is introduced, the reaction between isocyanate and mercapto proceeds simultaneously, which is not suitable.

By the way, the application of the pressure-sensitive adhesive as an adhesion modifier is also a typical example of the silane coupling agent. For example, the pressure-sensitive adhesive used when the liquid crystal cell and the optical film are attached is the size of a liquid crystal display (LCD). With the increase in size and widening, the required adhesion performance has become more sophisticated. In the case of LCDs, unlike the initial expectation that it would be difficult to increase the size to 20 inches or more, the size is rapidly increasing. The major manufacturers have been mainly producing small panels of 20 inches or less, but in response to the recent trends, they are actively introducing the latest technology and expanding the product range to large sizes of 20 inches or more. ..

As described above, in various optical films, the glass used at the time of manufacturing a liquid crystal display panel is becoming larger. However, when a defective product is generated during initial attachment and the optical film is removed from the liquid crystal cell and reused after cleaning the liquid crystal cell, if a conventional adhesive with high tackiness is used, strong adhesion will be obtained. Due to the force, not only is it difficult to remove the optical film again, but there is a high possibility of destroying an expensive liquid crystal cell, resulting in a problem that the production cost will be significantly increased.

Therefore, as LCDs have become larger, attempts have been made to develop highly functional adhesives that have various adhesive properties such as adhesiveness and reworkability. For example, Patent Documents 12 and 13 propose an acrylic pressure-sensitive adhesive composition containing an epoxy silane and an isocyanate silane for the purpose of providing a polarizing plate having excellent durability in a hot and humid environment.
Further, in Patent Documents 14 to 16, the initial adhesive force is low, the reworkability is excellent, the adhesive force is enhanced under high temperature and high humidity after pasting, and as an adhesive agent excellent in long-term durability, an alkoxy group at the polyether end is used. An acrylic pressure-sensitive adhesive containing an organosilicon compound having a silyl group has been proposed.

By using such a silane compound, the substrate and the polarizing plate can maintain an appropriate adhesive strength as required in the environment in which they are actually used, and the adhesive strength does not become excessively high due to heating or the like, It is said that the polarizing plate can be easily peeled off without damaging the liquid crystal element.

Further, as a technical trend in recent years, with the spread of touch sensor LCDs, a design in which an adhesive layer and a transparent electrode layer typified by indium tin oxide (ITO) are in direct contact has become mainstream. In such a product design, when a carboxylic acid group-containing acrylic polymer base, which has been the mainstream as an adhesive, is used, there is concern that ITO may corrode. Therefore, an adhesive based on an OH group-containing acrylic polymer is used instead. The technology has changed to the composition of agents.

However, in such an adhesive agent having an acid-free base polymer composition, the effect of the silane coupling agent, which was effective in the conventional adhesive agent, is limited, and the silane that contributes to exhibiting the same or higher level of performance. No coupling agent was found.

As described above, the isocyanate group-containing organosilicon compound is desired to have a simple and versatile production method, and in the use as a silane coupling agent, initial reworkability and high adhesive strength under high temperature and high humidity are required. It is desired to develop a well-balanced acid-free base polymer type pressure-sensitive adhesive that retains the following properties.

Japanese Patent Publication No. 5-8713 Japanese Patent Publication No. 5-8714 Japanese Patent No. 3806459 Japanese Patent Laid-Open No. 10-1486 Japanese Patent No. 2686420 Japanese Patent No. 2963309 Japanese Patent No. 4778844 Japanese Patent No. 5051354 Japanese Patent No. 5170414 International Publication No. 2012/070637 Japanese Patent No. 3164431 Japanese Patent No. 3022993 Patent No. 5595034 JP, 2011-219765, A Japanese Patent No. 4840888 International Publication No. 2010/26995

The present invention has been made in view of the above circumstances, and an isocyanate group-containing organosilicon compound capable of achieving both initial reworkability and high adhesive strength at high temperature or under high temperature and high humidity, and its simple and versatile production. The purpose is to provide a method.

The present inventor has conducted extensive studies in order to achieve the above-mentioned object, and an organic silicon compound having a polymerizable group and an isocyanate compound having a polymerizable group with respect to a compound having a plurality of mercapto groups in one molecule -By co-modifying by a thiol addition reaction, it is found that an organosilicon compound having a plurality of isocyanate groups in one molecule can be obtained, and the compound has compatibility with a resin and a bond with a matrix resin having a hydroxyl group. The present invention has been completed based on the finding that they have excellent properties in strength and interaction, and have suitable properties as an adhesive capable of achieving both initial reworkability and high adhesive strength at high temperature or under high temperature and high humidity.

（式中、Ｘは、炭素数１〜４の一価炭化水素基を表し、Ｒは、炭素数１〜６の一価炭化水素基を表し、Ａは、ヘテロ元素を含むまたはカルボニル基を含む、炭素数１５〜３０の３〜６価炭化水素基を表し、Ｂは、互いに独立して、エステル基を介してもよい炭素数２〜１０の二価炭化水素基を表し、ｎは、１〜３の整数を表し、ｐは１以上、ｑは２以上、かつ、ｐ＋ｑは３〜６の整数を表す。）
２． 下記一般式（２）で示される１のイソシアネート基含有有機ケイ素化合物、

（式中、Ｘ、Ｒ、Ａ、ｐ、ｑおよびｎは、前記と同義であり、Ｒ¹は、水素原子またはメチル基を表し、ｍは、１〜３の整数を表す。）
３． 下記一般式（３）で示される１のイソシアネート基含有有機ケイ素化合物、

（式中、Ｘ、Ｒ、Ｒ¹、Ａ、ｐ、ｑおよびｎは、前記と同義であり、ｌは、１〜１２の整数を表す。）
４． 前記Ｒ¹が、水素原子である２または３のイソシアネート基含有有機ケイ素化合物、
５． Ａが、下記一般式（４）〜（７）で表されるいずれかの基である１〜４のいずれかのイソシアネート基含有有機ケイ素化合物、

６． 下記一般式（８）

（式中、Ａは、前記と同義であり、ｒはＡの価数を表す。）
で示されるメルカプト基含有有機化合物と、下記一般式（９）

（式中、Ｚは、エステル基を介してもよい、不飽和二重結合を含む炭素数２〜１０の一価炭化水素基を表す。）
で示される不飽和二重結合含有イソシアネート化合物、および下記一般式（１０）

（式中、Ｘ、Ｒ、Ｚ、ｎは、前記と同義である。）
で示される不飽和二重結合含有有機ケイ素化合物を、ラジカル発生剤の存在下でエン−チオール付加反応させる１のイソシアネート基含有有機ケイ素化合物の製造方法、
７． １〜５のいずれかのイソシアネート基含有有機ケイ素化合物を含む接着剤、
８． （Ａ）アルコール性水酸基含有アクリル系ポリマー：１００質量部
（Ｂ）１〜５のいずれかのイソシアネート基含有有機ケイ素化合物：０．００１〜１０質量部、および
（Ｃ）多官能架橋剤：０．０１〜１０質量部
を含有する粘着剤、
９． １〜５のいずれかのイソシアネート基含有有機ケイ素化合物を含むコーティング剤、
１０． ９のコーティング剤で被覆または表面処理されてなる物品、
１１． ９のコーティング剤で、その表面が被覆または処理されたガラス繊維製品であって、ガラスクロス、ガラステープ、ガラスマットおよびガラスペーパーから選ばれるガラス繊維製品、
１２． ９のコーティング剤で、その表面が被覆または処理された無機フィラー、
１３． ９のコーティング剤で、その表面が被覆または処理されたセラミック、
１４． ９のコーティング剤で、その表面が被覆または処理された金属、
１５． 偏光フィルムと、この偏光フィルムの片面または両面に８の粘着剤から形成される粘着剤層とを有する粘着偏光板、
１６． 一対のガラス基板間に液晶が封入された液晶セルと、この液晶セルの片面または両面に貼着された１５の粘着偏光板とを有する液晶パネルを備える液晶表示装置
を提供する。 That is, the present invention is
1. An isocyanate group-containing organosilicon compound represented by the following general formula (1):

(In the formula, X represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and A contains a hetero element or a carbonyl group. Represents a C3 to C6 hydrocarbon group, B represents, independently of each other, a C2 to C10 divalent hydrocarbon group which may have an ester group interposed therebetween, and n represents 1 Represents an integer of 3; p represents 1 or more; q represents 2 or more; and p+q represents an integer of 3 to 6.)
2. 1, an isocyanate group-containing organosilicon compound represented by the following general formula (2),

(In the formula, X, R, A, p, q, and n have the same meanings as described above, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3.)
3. 1, an isocyanate group-containing organosilicon compound represented by the following general formula (3),

(In the formula, X, R, R ¹ , A, p, q, and n have the same meanings as described above, and l represents an integer of 1 to 12.)
4. 2 or 3 isocyanate group-containing organosilicon compound wherein R ¹ is a hydrogen atom,
5. A is an isocyanate group-containing organosilicon compound of any one of 1 to 4, which is any group represented by the following general formulas (4) to (7),

6. The following general formula (8)

(In the formula, A has the same meaning as above, and r represents the valence of A.)
A mercapto group-containing organic compound represented by the following general formula (9)

(In the formula, Z represents a monovalent hydrocarbon group having 2 to 10 carbon atoms and containing an unsaturated double bond, which may be via an ester group.)
An unsaturated double bond-containing isocyanate compound represented by the following general formula (10)

(In the formula, X, R, Z, and n are as defined above.)
A method for producing an isocyanate group-containing organosilicon compound according to 1, which comprises subjecting an unsaturated double bond-containing organosilicon compound represented by to an ene-thiol addition reaction in the presence of a radical generator,
7. An adhesive containing the isocyanate group-containing organosilicon compound according to any one of 1 to 5,
8. (A) Alcoholic hydroxyl group-containing acrylic polymer: 100 parts by mass (B) Any of the isocyanate group-containing organosilicon compounds of 1 to 5: 0.001 to 10 parts by mass, and (C) Polyfunctional crosslinking agent: 0. An adhesive containing 01 to 10 parts by mass,
9. A coating agent containing the isocyanate group-containing organosilicon compound according to any one of 1 to 5,
10. Articles coated or surface-treated with the coating agent of item 9,
11. A glass fiber product, the surface of which is coated or treated with the coating agent of 9, which is selected from glass cloth, glass tape, glass mat and glass paper,
12. An inorganic filler whose surface is coated or treated with the coating agent of 9,
13. Ceramic whose surface is coated or treated with the coating agent of 9;
14. A metal whose surface is coated or treated with the coating agent of 9;
15. An adhesive polarizing plate having a polarizing film and an adhesive layer formed from the adhesive of 8 on one side or both sides of the polarizing film,
16. Provided is a liquid crystal display device including a liquid crystal panel having a liquid crystal cell in which a liquid crystal is sealed between a pair of glass substrates, and 15 adhesive polarization plates attached to one side or both sides of the liquid crystal cell.

The isocyanate group-containing organosilicon compound of the present invention contains a specific connecting structure in which a sulfur atom is necessarily contained in the connecting chain of the isocyanate group and the hydrolyzable silyl group, and therefore, the silane cup used in the existing technology. Compared to the ring agent, the hydrophobicity increases, the proportion of the organic part occupies increases, and because it has multiple isocyanate groups that serve as binding points with the organic resin, it becomes highly reactive, resulting in improved compatibility with the resin. However, since the bonding force and interaction with the matrix resin having a hydroxyl group are excellent, the adhesiveness between the adhesive containing the matrix resin and the substrate can be dramatically improved.
By blending the isocyanate group-containing organosilicon compound of the present invention having such characteristics as an essential component of the adhesion modifier, the initial adhesive strength at the time of sticking is excellent and the reworkability is excellent, and high temperature after sticking or The advantage is that after passing through high temperature and high humidity treatment, the adhesive strength with the adherend increases and provides a pressure-sensitive adhesive layer with excellent long-term durability, and does not corrode easily corroded adherends such as ITO. have.
Therefore, the isocyanate group-containing organosilicon compound of the present invention is useful as one component of adhesives, pressure-sensitive adhesives, inorganic fillers, coating agents used for surface treatment of ceramics, metals, glass fibers, etc. It is useful as an adhesive layer of an adhesive polarizing plate used for a display device.
Further, the method for producing an isocyanate group-containing organosilicon compound of the present invention is simpler than the previously known methods for producing an isocyanate silane while using easily available existing industrial raw materials, and has excellent productivity. Is.

3 is an IR spectrum of the compound (15) obtained in Example 1. 1 is a ¹ H-NMR spectrum of the compound (15) obtained in Example 1. 3 is an IR spectrum of the compound (18) obtained in Example 4. 3 is a ¹ H-NMR spectrum of the compound (18) obtained in Example 4.

Hereinafter, the present invention will be specifically described.
The isocyanate group-containing organosilicon compound according to the present invention is represented by the following general formula (1).

In formula (1), X represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and A represents a hetero element or a carbonyl group. And a C3 to C6 hydrocarbon group having 15 to 30 carbon atoms, B is independently of each other a C2 to C10 divalent hydrocarbon group optionally having an ester group, and n is , 1 to 3, p is 1 or more, q is 2 or more, and p+q is an integer of 3 to 6.

Specific examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms in X include alkyl groups such as methyl, ethyl, n-propyl and butyl groups, and a polymerizable group-containing silane coupling agent as a reaction raw material. Considering availability and the like, methyl and ethyl groups are preferable.
The monovalent hydrocarbon group having 1 to 6 carbon atoms in R may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, n-butyl and n-pentyl. , An alkyl group such as n-hexyl group, a phenyl group and the like, but in view of the availability of the polymerizable group-containing silane coupling agent as a reaction raw material, the methyl group is preferable.

Specific examples of the C 3 to C 6 hydrocarbon group having a hetero atom containing 15 to 30 carbon atoms or the C 3 to C 6 hydrocarbon group containing a carbonyl group having a carbon number of 15 to 30 are particularly limited. However, considering the availability of the mercapto group-containing organic compound as a reaction raw material described later, any group represented by the following general formulas (4) to (7) is preferable.

The divalent hydrocarbon group having 2 to 10 carbon atoms in the divalent hydrocarbon group having 2 to 10 carbon atoms, which may have an ester group in B, may be linear, branched or cyclic. Examples include alkylene groups such as ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decylene groups.
Specific examples of the divalent hydrocarbon group having 2 to 10 carbon atoms through an ester group include 3-one-4-oxa-hexane-1,6-diyl and 2-methyl-3-one-4-oxa. -Hexane-1,6-diyl, 3-one-4-oxa-octane-1,8-diyl, 2-methyl-3-one-4-oxa-octane-1,8-diyl, 3-one-4 Examples thereof include -oxa-decane-1,10-diyl, 2-methyl-3-one-4-oxa-decane-1,10-diyl group and the like.
Among these, ethylene, trimethylene, propylene, hexamethylene, octamethylene, 3- On-4-oxa-hexane-1,6-diyl and 2-methyl-3-one-4-oxa-hexane-1,6-diyl are preferable, and ethylene, 3-one-4-oxa-hexane-1, A 6-diyl, 2-methyl-3-one-4-oxa-hexane-1,6-diyl group is more preferred.

Therefore, as the isocyanate group-containing organosilicon compound of the present invention, those represented by the formula (2) or the formula (3) are preferable, and in particular, A is any of the formulas (4) to (7). More preferably, the following R ¹ is a hydrogen atom.

（式中、Ｘ、Ｒ、Ａ、ｐ、ｑおよびｎは、上記と同義であり、Ｒ¹は、水素原子またはメチル基を表し、ｍは、１〜３の整数を表し、ｌは、１〜１２、好ましくは２〜１０の整数を表す。）

(In the formula, X, R, A, p, q and n have the same meanings as described above, R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 3, and 1 represents 1 ~ 12, preferably an integer of 2 to 10).

In each of the above formulas, p is 1 or more, q is 2 or more, and p+q is an integer of 3 to 6, q is preferably 3 or more, and p+q is preferably 4 or more.

The isocyanate group-containing organosilicon compound of the present invention described above is a mercapto group-containing organic compound represented by the following general formula (8), an unsaturated double bond-containing isocyanate compound represented by the following general formula (9), and The unsaturated double bond-containing organosilicon compound represented by the general formula (10) can be obtained by an ene-thiol addition reaction in the presence of a radical generator.

（式中、Ａ、Ｘ、Ｒ、Ｚおよびｎは、上記と同義であり、ｒはＡの価数を表し、Ｚは、エステル基を介してもよい、不飽和二重結合を含む炭素数２〜１０の一価炭化水素基を表す。）

(In the formula, A, X, R, Z and n have the same meanings as described above, r represents the valence of A, and Z is the number of carbon atoms containing an unsaturated double bond, which may be through an ester group. It represents a monovalent hydrocarbon group of 2 to 10.)

More specifically, a mercapto group and a carbon-carbon double bond are subjected to an addition reaction to form a thioether bond by the following reaction formula, thereby forming a silane coupling agent containing a hydrolyzable silyl group and an isocyanate structure. can get.

A and r in the above formula (8) are as described above, and among them, as the readily available mercapto group-containing organic compound represented by the formula (8), the following general formulas (11) to (14) are given. However, the compounds are not limited to these.

The unsaturated double bond-containing isocyanate compound represented by the above formula (9) is not particularly limited, but from the viewpoint of easy availability, allyl isocyanate, 2-isocyanatoethyl acrylate, 2- Isocyanatoethyl methacrylate and the like are preferable, and among them, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate, which have low toxicity and are easy to handle, are more preferable, and 2-isocyanatoethyl acrylate having high ene-thiol reactivity is preferable. Even more preferred is latte.

Specific examples of the unsaturated double bond-containing organosilicon compound represented by the above formula (10) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane and vinyl. Dimethylethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyldimethylmethoxysilane, allyltriethoxysilane, allylmethyldiethoxysilane, allyldimethylethoxysilane, hexenyltrimethoxysilane, hexenylmethyldimethoxysilane, hexenyldimethylmethoxysilane, Hexenyltriethoxysilane, hexenylmethyldiethoxysilane, hexenyldimethylethoxysilane, octenyltrimethoxysilane, octenylmethyldimethoxysilane, octenyldimethylmethoxysilane, octenyltriethoxysilane, octenylmethyldiethoxysilane, octenyldimethyl Ethoxysilane, norbornenylethyltrimethoxysilane, norbornenylethylmethyldimethoxysilane, norbornenylethyldimethylmethoxysilane, norbornenylethyltriethoxysilane, norbornenylethylmethyldiethoxysilane, norbornenylethyldimethylethoxy Silane, (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, (meth)acryloxypropyldimethylmethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxypropylmethyldi Ethoxysilane, (meth)acryloxypropyldimethylethoxysilane, (meth)acryloxytrimethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxymethyldimethylmethoxysilane, (meth)acryloxymethyltriethoxysilane Silane, (meth)acryloxymethylmethyldiethoxysilane, (meth)acryloxymethyldimethylethoxysilane, (meth)acryloxyoctyltrimethoxysilane, (meth)acryloxyoctylmethyldimethoxysilane, (meth)acryloxyoctyldimethyl Methoxysilane, (meth)acryloxyoctyltriethoxysilane, (meth)acryloxyoctylmethyldiethoxysilane, (meth)acryloxyoctyldimethylethoxysilane and the like are mentioned, and are easily available, Vinyltrimethoxysilane, vinyltriethoxysilane, (meth)acryloxypropyltrimethoxysilane and the like are preferable, and among them, vinyltrimethoxysilane having a low material cost and rich ene-thiol reactivity is more preferable.

Reaction of the mercapto group-containing organic compound represented by the above formula (8) with the unsaturated double bond-containing isocyanate compound represented by the formula (9) and the unsaturated double bond-containing organosilicon compound represented by the formula (10) The ratio is preferably such that the mercapto group becomes 0.9 to 1.1 mol, and particularly preferably 0.95 to 1.05 mol, relative to 1 mol of the unsaturated hydrocarbon double bond.

Examples of the radical generator include a thermal radical generator and a photo radical generator, and a thermal radical generator such as an azo compound and a peroxide is preferable.
Specific examples of the heat radical generator include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide. (Benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (t-butyl peracetate, t-butyl peroxyoctoate, t-butyl peroxybenzoate, and other alkyl percarboxylic acid esters) Etc.), organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds (2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis( Isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc.), azoamide compound (2,2') -Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} etc.), azoamidine compound (2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, etc.), azoalkane compounds (2,2′-azobis(2,4,4-trimethylpentane), 4,4′ -Azobis(4-cyanopentanoic acid) etc.), azo compounds having an oxime skeleton (2,2'-azobis(2-methylpropionamide oxime) etc.) and the like, and these are used alone. Also, two or more kinds may be used in combination.

Specific examples of the photo radical generator include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin alkyl ethers); acetophenones (acetophenone, p-dimethylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl- 2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc.); propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propiophenone, 2,2) -Dimethoxy-1,2-diphenylethan-1-one etc.); butyrylphenones (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one, etc.); aminoacetophenones (2-methyl- 2-morpholino(4-thiomethylphenyl)propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2 -Methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 1-(4-butylphenyl)-2- Dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthio (Phenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, etc.); benzophenones (benzophenone, benzyl, N,N′-bis(dimethyl) Amino)benzophenone (Michler's ketone), 3,3- N,N'-dialkylaminobenzophenone such as dimethyl-4-methoxybenzophenone); ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal etc.); thioxanthenes (thioxanthene, 2-chlorothioxanthene, 2,4-diethyl) Anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (thio)xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2) , 4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; acridines (1,3-bis-(9-acridinyl)propane, 1,7-bis-(9-acridinyl)heptane, 1 , 5-bis-(9-acridinyl)pentane, etc.); triazines (2,4,6-tris(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) )-S-Triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, etc.); sulfides (benzyldiphenylsulfide, etc.); acylphosphine oxides ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like); titanocenes; oxime esters and the like, and these may be used alone or in combination of two or more kinds.

The amount of the radical generator used is 100 parts by mass based on the total amount of the mercapto group-containing organic compound, the unsaturated hydrocarbon double bond structure group-containing isocyanate compound and the unsaturated hydrocarbon double bond structure group-containing organosilicon compound. 0.01 to 15 parts by mass is preferable, and 0.1 to 10 parts by mass is more preferable.

Although the reaction temperature is not particularly limited, 25 to 120° C. is preferable, and 60 to 100° C. is preferable in view of suppressing side reactions such as polymerization of olefin compounds while keeping the reaction rate moderate. More preferable.
The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

The addition order of the reaction substrate in the above reaction is not particularly limited, in consideration of suppressing side reactions such as homopolymerization of the unsaturated double bond-containing compound and efficiently obtaining the target product, the formula ( In the presence of the mercapto group-containing organic compound represented by 8) and the radical generator, the unsaturated double bond group-containing compound represented by the formulas (9) and (10) is preferably added dropwise for reaction.

In addition, a solvent that does not react with the mercapto group, the isocyanate group, and the unsaturated carbon-carbon double bond can be used in the above reaction.
Specific examples of such a solvent include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; aromatic solvents such as benzene, toluene, xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ethyl acetate, butyl acetate, ester solvents such as lactones, diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, ether solvents such as 1,4-dioxane, and the like, among which industrially Toluene and xylene, which are easily available, are preferable.

When the isocyanate group-containing organosilicon compound of the present invention is used as a coating agent or a primer, it may contain a solvent, if necessary.
In this case, the content of the isocyanate group-containing organosilicon compound is preferably 0.1 to 90% by mass, and more preferably 1 to 50% by mass based on the whole coating agent or primer. The balance is the solvent as the optional component.
As the solvent, those similar to the above reaction solvent can be used.

The base material coated or treated with the coating agent or primer containing the isocyanate group-containing organosilicon compound of the present invention is generally an inorganic material that reacts with a hydrolyzable silyl group to form a bond, or an organic material that reacts with an isocyanate group to bond. Any resin can be applied without limitation, and the shape of the substrate is not particularly limited.
Examples of typical inorganic materials include inorganic fillers such as silica; glass fiber products such as glass cloth, glass tape, glass mat and glass paper; ceramics; metal substrates.
In addition, typical organic resins include, for example, polyether, polyvinyl alcohol, hydroxyl group-containing acrylic resin, epoxy resin, phenol resin, polyimide resin, unsaturated polyester resin, and the like.

The pressure-sensitive adhesive of the present invention contains the following components (A) to (C).
(A) Alcoholic hydroxyl group-containing acrylic polymer ((meth)acrylic copolymer): 100 parts by mass (B) Isocyanate group-containing organosilicon compound: 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass (C) polyfunctional crosslinking agent: 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass

Thus, by blending 0.001 to 10 parts by mass of the isocyanate group-containing organosilicon compound (B) with 100 parts by mass of the (A) alcoholic hydroxyl group-containing acrylic polymer, a desired adhesiveness-modifying effect is imparted. At the same time, the effect of improving the initial adhesiveness can be suppressed, and the cost increase due to the addition can be suppressed.
Further, by blending 0.01 to 10 parts by mass of the (C) polyfunctional crosslinking agent with respect to 100 parts by mass of the component (A), aggregation can be prevented while imparting a desired adhesiveness-modifying effect. Molding into an adhesive sheet or the like becomes easy.
The pressure-sensitive adhesive of the present invention is a (meth)acrylic pressure-sensitive adhesive containing a silane coupling agent having an isocyanate group containing a sulfur atom in the connecting chain, and has a low initial adhesive strength when attached to glass, ITO or the like, It has excellent reworkability, and its adhesive strength after moist heat treatment after attachment is sufficiently high, resulting in excellent long-term durability.

Examples of the alcoholic hydroxyl group-containing acrylic polymer as the component (A) include copolymers of an alcoholic hydroxyl group-containing (meth)acrylic monomer and a (meth)acrylic acid alkyl ester monomer, and a known copolymerization procedure is used. Can be manufactured.
As the alcoholic hydroxyl group-containing (meth)acrylic monomer, those available as general industrial products may be used, and specific examples thereof include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.
The (meth)acrylic acid alkyl ester may also be available as a general industrial product, and specific examples thereof include those having an alkyl group of a methyl group, an ethyl group, a propyl group, and a butyl group.
The content ratio of the alcoholic hydroxyl group-containing (meth)acrylic monomer unit with respect to all the monomer units in the above-mentioned copolymer imparts desired adhesiveness and suppresses viscosity increase and aggregation to improve moldability into a sheet or the like. In consideration of the above, the range of 0.1 to 50 mol% is preferable, and the range of 1 to 20 mol% is more preferable.

The polyfunctional crosslinking agent as the component (C) plays a role of increasing the cohesive force of the pressure-sensitive adhesive by reacting with a carboxyl group, a hydroxyl group or the like.
As the polyfunctional crosslinking agent, isocyanate-based, epoxy-based, aziridine-based, metal chelate-based crosslinking agents and the like can be used, and among them, isocyanate-based crosslinking agents are suitable for use.
Specific examples of the isocyanate cross-linking agent include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoform diisocyanate, tetramethyl xylene diisocyanate, naphthalene diisocyanate, and a reaction product of these with a polyol such as trimethylolpropane (trimethyldipropane). Methylolpropane tolylene diisocyanate adduct etc.) and the like.

Specific examples of the epoxy-based cross-linking agent include ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N′,N′-tetraglycidyl ethylenediamine, glycerin diglycidyl ether, glycerin triglycidyl ether, and polyglycerin polyglycerin. Examples thereof include glycidyl ether and sorbitol-based polyglycidyl ether.
Specific examples of the aziridine-based cross-linking agent include N,N'-toluene-2,4-bis(1-aziridinecarboxide) and N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxide). , Triethylenemelamine, bisisoprotaroyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide and the like.
Specific examples of the metal chelate-based cross-linking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and vanadium is coordinated with acetylacetone or ethyl acetoacetate.

The method for producing the pressure-sensitive adhesive of the present invention is not particularly limited, and it can be obtained by mixing the above-mentioned components (A) to (C) by a usual method.
The mixing conditions are not particularly limited, but are preferably 10 to 150° C. for 10 minutes to 10 hours.
In this case, the above-mentioned isocyanate group-containing organosilicon compound can be used by adding it in the compounding step after the polymerization of the (meth)acrylic copolymer, and during the production step of the (meth)acrylic copolymer. Even if added, the same effect is shown.
Further, the polyfunctional cross-linking agent enables uniform coating when the functional group cross-linking reaction of the cross-linking agent hardly occurs in the compounding process performed for forming the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition. Become. After coating and drying and aging, a crosslinked structure is formed to give an adhesive layer having elasticity and strong cohesive force.

The pressure-sensitive adhesive thus obtained is applied to an adherend such as a glass plate, a plastic film, or a paper, and is applied at 25 to 150° C. and 20 to 90% RH for 5 minutes to 5 hours, particularly 40 to 80° C. The pressure-sensitive adhesive layer can be formed by curing at 25 to 60% RH for 10 minutes to 3 hours.

Further, the pressure-sensitive adhesive of the present invention is applied to one side or both sides of a polarizing film or a polarizing element to form a pressure-sensitive adhesive layer, whereby the polarizing film or the polarizing element and the above-mentioned one side or both sides of the polarizing film or the polarizing element. An adhesive polarizing plate having an adhesive layer formed of an adhesive is obtained.
The polarizing film or the polarizing element forming the polarizing plate is not particularly limited. An example of the polarizing film is a film obtained by stretching a film made of a polyvinyl alcohol-based resin with a polarizing component such as iodine or a heterochromatic dye.
The thickness of these polarizing films and the like is not limited, and they can be formed into a normal thickness.
As the polyvinyl alcohol-based resin, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and a saponified product of an ethylene/vinyl acetate copolymer are used.

There is no particular limitation on the method of forming the pressure-sensitive adhesive layer on the polarizing film, a method of directly applying the pressure-sensitive adhesive to the surface of the polarizing film using a bar coater or the like, and drying the pressure-sensitive adhesive once releasing substrate. It is possible to employ a method in which, after coating on the surface and drying, the pressure-sensitive adhesive layer formed on the surface of the releasable substrate is transferred to the surface of the polarizing film and then aged. In this case, drying is preferably at 25 to 150° C., 20 to 90% RH for 5 minutes to 5 hours, and aging is preferably at 25 to 150° C., 20 to 90% RH for 5 minutes to 5 hours.

Although the thickness of the pressure-sensitive adhesive layer is not particularly limited, 0.01 to 100 μm is preferable, and 0.1 to 50 μm is more preferable, in view of sufficiently exerting the effect as the pressure-sensitive adhesive layer and suppressing the cost increase. preferable.

The polarizing film (adhesive polarizing plate) having the adhesive layer thus obtained is provided with a layer providing an additional function such as a protective layer, a reflective layer, a retardation plate, an optical viewing angle compensation film, and a brightness enhancement film. One or more types can be laminated.
For example, on both surfaces of a polarizing film having an adhesive layer, a cellulose-based film such as triacetyl cellulose; a polyester-based film such as a polycarbonate film or a polyethylene terephthalate film; a polyethersulfone-based film; polyethylene, polypropylene, or a copolymer of these. It is possible to form a multilayer film in which protective films such as polyolefin films are laminated.
At this time, the thickness of these protective films is not particularly limited, and the protective film can be formed into a normal thickness.

The adhesive polarizing plate is particularly applicable to general liquid crystal display devices in general, and the type of liquid crystal panel is not particularly limited.
In particular, it is preferable to configure a liquid crystal display device including a liquid crystal panel in which the adhesive polarizing plate of the present invention is attached to one side or both sides of a liquid crystal cell in which liquid crystal is sealed between a pair of glass substrates.

Furthermore, the pressure-sensitive adhesive of the present invention, in addition to the above-mentioned polarizing film, industrial sheets, particularly reflective sheets, structural pressure-sensitive adhesive sheets, photographic pressure-sensitive adhesive sheets, lane-display pressure-sensitive adhesive sheets, optical pressure-sensitive adhesive products, electronic components, etc., It can be used for any purpose.
Further, it can be applied to a laminated product having a multilayer structure, that is, a general commercial adhesive sheet product, a medical patch, a heat activation product, and the like, which have the same working concept.

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples.
The apparatus used in the examples is as follows. Further, the specific gravity and the refractive index are values measured at 25°C.
IR: Thermo Scientific NICOLET6700
¹ H-NMR: AVANCE400M manufactured by Bruker
GPC: Tosoh HLC-8220GPC
Viscosity (25℃): Capillary kinematic viscometer

[1] Synthesis of Test Polymer [Synthesis Example 1] Synthesis of Polyurethane Elastomer for Adhesion Test 150 parts by mass of polyoxytetramethylene glycol having a number average molecular weight of 1,000, 100 parts by mass of 1,6-xylene glycol, and water. 5 parts by mass, 200 parts by mass of hexamethylene diisocyanate and 800 parts by mass of dimethylformamide were mixed with stirring and heated to 90° C., and the reaction was carried out by stirring for 2 hours, and then 3 parts by mass of dibutylamine was added to react. Was stopped, and then excess amine was neutralized with acetic anhydride to obtain a polyurethane elastomer.

[Synthesis Example 2] Synthesis of acrylic polymer for adhesive test In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 98.1 g of n-butyl acrylate (BA) and 4-hydroxybutyl were added. 0.6 g of acrylate (4-HBA) and 1.3 g of 2-hydroxyethyl methacrylate (2-HEMA) were placed, and 100 g of ethyl acetate was charged and dissolved as a solvent. Then, nitrogen gas bubbling was carried out for 1 hour to remove oxygen, the reaction system was replaced with nitrogen, and the temperature was maintained at 62°C. 0.03 g of azobisisobutyronitrile as a polymerization initiator was added to this with stirring, and the mixture was reacted at 62° C. for 8 hours to give a (meth)acrylic copolymer as an acrylic polymer (base polymer). Obtained.

[2] Production of Organosilicon Compound Containing Isocyanate Group [Example 1] Production of Compound (15)

In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 488 g (1 mol) of a mercapto group-containing organic compound represented by the following formula (12) and 2,2′-azobis(2- 2 g of methylbutyronitrile) was charged and heated to 90°C. 423 g (3 mol) of acryloxyethyl isocyanate was added dropwise thereto. The reaction was exothermic, and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. After the dropping was completed, 148 g (1 mol) of vinyltrimethoxysilane was subsequently added dropwise. The reaction was exothermic, and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. The mixture was heated and stirred at 90° C. for 1 hour, and it was confirmed by gas chromatography (GC) that the peak derived from the raw material vinyltrimethoxysilane disappeared, and the reaction was terminated. The obtained reaction product was a pale yellow liquid, had a viscosity of 909.9 mm ² /s, a specific gravity of 1.28 and a refractive index of 1.508. When ¹ H-NMR was measured for this reaction product, The isocyanate group-containing organosilicon compound represented was obtained. The IR spectrum and ¹ H-NMR spectrum of the compound (15) are shown in FIGS. 1 and 2.

[Example 2] Production of compound (16)

With respect to 488 g (1 mol) of the mercapto group-containing organic compound used in Example 1, 282 g (2 mol) of acryloxyethyl isocyanate as a reaction raw material and 296 g (2 mol) of vinyltrimethoxysilane were used except that the reaction ratio was changed. An isocyanate group-containing organosilicon compound was obtained in the same manner as in Example 1. When ¹ H-NMR was measured for this reaction product, it was an isocyanate group-containing organosilicon compound represented by the formula (16).

[Example 3] Production of compound (17)

An isocyanate group-containing organosilicon compound was obtained in the same manner as in Example 1, except that the vinyltrimethoxysilane used in Example 1 was changed to 7-octenyltrimethoxysilane. When ¹ H-NMR was measured for this reaction product, it was an isocyanate group-containing organosilicon compound represented by the formula (17).

[Example 4] Production of compound (18)

In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 783 g (1 mol) of a mercapto group-containing organic compound represented by the following formula (13) and 2,2′-azobis(2- 3 g of methylbutyronitrile) was charged and heated to 90°C. 705 g (5 mol) of acryloxyethyl isocyanate was added dropwise thereto. The reaction was exothermic and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. After the dropping was completed, 148 g (1 mol) of vinyltrimethoxysilane was subsequently added dropwise. The reaction was exothermic and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. The mixture was heated and stirred at 90° C. for 1 hour, and it was confirmed by GC measurement that the peak derived from vinyltrimethoxysilane as a raw material had disappeared, and the reaction was terminated. The obtained reaction product was a pale yellow liquid, had a viscosity of 5,252.3 mm ² /s, a specific gravity of 1.29 and a refractive index of 1.514. When ¹ H-NMR was measured for this reaction product, the formula (18 ) Was an organosilicon compound containing an isocyanate group. The IR spectrum and ¹ H-NMR spectrum of the compound (18) are shown in FIGS. 3 and 4.

Example 5 Production of compound (19)

With respect to 783 g (1 mol) of the mercapto group-containing organic compound used in Example 4, 564 g (4 mol) of acryloxyethyl isocyanate as a reaction raw material and 296 g (2 mol) of vinyltrimethoxysilane were used, except that the reaction ratio was changed. An isocyanate group-containing organosilicon compound was obtained in the same manner as in Example 4. When ¹ H-NMR was measured for this reaction product, it was an isocyanate group-containing organosilicon compound represented by the formula (19).

[Example 6] Production of compound (20)

With respect to 783 g (1 mol) of the mercapto group-containing organic compound used in Example 4, 282 g (2 mol) of acryloxyethyl isocyanate as a reaction raw material and 592 g (4 mol) of vinyltrimethoxysilane were used, except that the reaction ratio was changed. An isocyanate group-containing organosilicon compound was obtained in the same manner as in Example 4. When ¹ H-NMR was measured for this reaction product, it was an isocyanate group-containing organosilicon compound represented by the formula (20).

[Example 7] Production of compound (21)

An isocyanate group-containing organosilicon compound was obtained in the same manner as in Example 4, except that the vinyltrimethoxysilane used in Example 4 was changed to 7-octenyltrimethoxysilane. When ¹ H-NMR was measured for this reaction product, it was an isocyanate group-containing organosilicon compound represented by the formula (21).

[Example 8] Production of compound (22)

In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 525 g (1 mol) of a mercapto group-containing organic compound represented by the following formula (14) and 2,2′-azobis(2- 2 g of methylbutyronitrile) was charged and heated to 90°C. 282 g (2 mol) of acryloxyethyl isocyanate was added dropwise thereto. The reaction was exothermic, and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. After the dropping was completed, 148 g (1 mol) of vinyltrimethoxysilane was subsequently added dropwise. The reaction was exothermic, and the dropping rate was adjusted so that the internal temperature did not exceed 95°C. The mixture was heated and stirred at 90° C. for 1 hour, and it was confirmed by GC measurement that the peak derived from vinyltrimethoxysilane as a raw material had disappeared, and the reaction was completed. The reaction product obtained was a pale yellow liquid, had a viscosity of 744.1 mm ² /s, a specific gravity of 1.29 and a refractive index of 1.522. When ¹ H-NMR was measured for this reaction product, The isocyanate group-containing organosilicon compound represented was obtained.

[Primer adhesion test]
For the glass plate, the organosilicon compound obtained in Examples 1 to 8 above, isocyanate propyltrimethoxysilane (Comparative Example 1) and one isocyanate group in one molecule of the following formula (23) were contained and hydrolyzed. A silane coupling agent (Comparative Example 2) containing a sulfur atom in the chain connecting to the silyl group is applied with a brush using a toluene solution containing 10% by mass of each, and dried at 80° C. for 5 minutes, and then at room temperature (23 C.), the polyurethane elastomer obtained in Synthesis Example 1 was applied with a brush, and dried at 100.degree. C. for 10 minutes. Then, the resulting coating film is cut into vertical and horizontal cuts at 1 mm intervals to form 100 cross-cuts, which are then pressure-bonded with cellophane tape and then peeled off. The number of peeled cross-cuts indicates the urethane resin of the primer. And the adhesiveness with an inorganic base material was evaluated. The results are shown in Table 1. In addition, Table 1 also shows an example in which the primer is not applied.

As shown in Table 1, with respect to the primer containing the organosilicon compound obtained in Examples 1 to 8, there is no cross-cut in any of the substrates, and the adhesive performance is extremely good. I understand.

[3] Preparation and Evaluation of Adhesive [Examples 9 to 16 and Comparative Examples 3 to 7]
(B) Adhesion modifier: silane coupling obtained in Examples 1 to 8 with respect to 100 parts by weight of (A) acrylic polymer: (meth) acrylic copolymer obtained in Synthesis Example 2. Agents or the organosilicon compounds of Comparative Examples 1 and 2 and (C) a trimethylolpropane tolylene diisocyanate adduct (TDI) as a cross-linking agent are mixed in the respective compositional compositions shown in Tables 2 and 3 to prepare pressure-sensitive adhesive compositions. did.

The obtained pressure sensitive adhesive was coated on release paper and dried to prepare a uniform pressure sensitive adhesive layer of 25 μm. The pressure-sensitive adhesive layer was applied to an iodine-based polarizing plate having a thickness of 185 μm, and the obtained polarizing plate was cut into an appropriate size and used for each evaluation.
The test pieces of the manufactured polarizing plates were evaluated for durability reliability, glass adhesion, reworkability, and changes in adhesion under heat and moisture/heat resistance conditions through the following evaluation test methods. The results are shown in Table 4.

(1) Durability and reliability A polarizing plate (90 mm x 170 mm) coated with an adhesive was attached to a glass substrate (110 mm x 190 mm x 0.7 mm) with the optical absorption axes crossed on both sides. At this time, the pressure applied was about 5 kgf/cm ³ , and the work was carried out in a clean room so that bubbles and foreign matter were not generated.
In order to evaluate the moisture resistance and heat resistance of this test piece, it was left for 1,000 hours under the conditions of 60° C./90% RH, and then the presence or absence of bubbles or peeling was confirmed. Regarding the heat resistance, after leaving it at 80° C./30% RH for 1,000 hours, the state of bubbles and peeling was observed. In addition, before evaluating the state of the test piece, it is left to stand at room temperature (23° C./60% RH) for 24 hours.
The evaluation criteria for durability evaluation are as follows.
○: No bubbles or peeling phenomenon △: There were few bubbles or peeling phenomenon ×: There were many bubbles or peeling phenomenon (2) Glass adhesive strength At room temperature (23°C/60%RH), a polarizing plate coated with a pressure-sensitive adhesive was used. After aging for 7 days, each of the polarizing plates was cut into a size of 1 inch×6 inch and attached to a 0.7 mm thick non-alkali glass using a 2 kg rubber roller. After storing at room temperature for 1 hour, the initial adhesive strength was measured, then aging was performed at 50° C. for 4 hours, and after storing at room temperature for 1 hour, the adhesive strength was measured.
(3) Reworkability A polarizing plate (90 mm x 170 mm) coated with an adhesive was attached to a glass substrate (110 mm x 190 mm x 0.7 mm), and then left at room temperature (23°C/60%RH) for 1 hour. After aging at 50° C. for 4 hours and allowing to cool at room temperature for 1 hour, the polarizing plate was peeled from the glass.
The evaluation was performed as follows, based on whether or not the polarizing plate or the glass plate could be peeled off without leaving the adhesive on the glass surface without breaking.
○: Easy re-peeling △: Re-peeling is a little difficult (adhesive remains on the glass surface)
×: Cannot be peeled (glass or polarizing plate is damaged)

As shown in Table 4, the pressure-sensitive adhesives prepared in Examples 9 to 16 are excellent in initial reworkability, exhibit sufficient adhesive force with glass by high temperature and high temperature and high humidity treatment, and have long-term durability. It turns out to be excellent.
On the other hand, Comparative Example 3 does not contain an adhesion modifier, and thus it can be seen that sufficient adhesion is not exhibited after heat curing.
Comparative Example 4 uses a conventional silane coupling agent containing an isocyanate propyl group, but the isocyanate group-silyl connecting chain of this compound is a propylene group, and the initial molecule has a low hydrophobicity, and thus has an initial adhesive force. Although the reworkability of No. 1 is exhibited, it is understood that the final adhesion strength after curing is insufficient because the compatibility with the resin is relatively insufficient.
Comparative Example 5 is a silane coupling agent having a structure similar to that of the present invention having a sulfur atom in the isocyanate group-silyl group connecting chain. However, since there is one isocyanate group in one molecule, there are few reaction points, It can be seen that the adhesion strength after 4 hours at ℃ is insufficient and the durability reliability is also insufficient.
In Comparative Example 6, the amount of the component (B) used was too small, so that the effect was insufficient. On the other hand, in Comparative Example 6, the amount of the component (B) used was too large, so that excessive adhesion was exhibited from the initial stage, resulting in poor reworkability. You can see that it is enough.

Claims (16)

An isocyanate group-containing organosilicon compound represented by the following general formula (1).

(In the formula, X represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and A contains a hetero element or a carbonyl group. Represents a C3 to C6 trivalent hydrocarbon group, B represents, independently of each other, a C2 to C10 divalent hydrocarbon group which may have an ester group interposed therebetween, and n represents 1 Represents an integer of 3 or more, p represents 1 or more, q represents 2 or more, and p+q represents an integer of 3 to 6.) The isocyanate group-containing organosilicon compound according to claim 1, which is represented by the following general formula (2).

(In the formula, X, R, A, p, q and n have the same meanings as described above, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3.) The isocyanate group-containing organosilicon compound according to claim 1, which is represented by the following general formula (3).

(In the formula, X, R, R ¹ , A, p, q, and n have the same meanings as described above, and l represents an integer of 1 to 12.) The isocyanate group-containing organosilicon compound according to claim 2, wherein R ¹ is a hydrogen atom. The isocyanate group-containing organosilicon compound according to any one of claims 1 to 4, wherein A is any group represented by the following general formulas (4) to (7).

The following general formula (8)

(In the formula, A has the same meaning as above, and r represents the valence of A.)
A mercapto group-containing organic compound represented by the following general formula (9)

(In the formula, Z represents a monovalent hydrocarbon group having 2 to 10 carbon atoms and containing an unsaturated double bond, which may be via an ester group.)
An unsaturated double bond-containing isocyanate compound represented by the following general formula (10)

(In the formula, X, R, Z, and n are as defined above.)

The method for producing an isocyanate group-containing organosilicon compound according to claim 1, wherein the unsaturated double bond-containing organosilicon compound represented by (1) is subjected to an ene-thiol addition reaction in the presence of a radical generator. An adhesive containing the isocyanate group-containing organosilicon compound according to claim 1. (A) Alcoholic hydroxyl group-containing acrylic polymer: 100 parts by mass (B) Isocyanate group-containing organosilicon compound according to any one of claims 1 to 5: 0.001 to 10 parts by mass, and (C) polyfunctional Crosslinking agent: An adhesive containing 0.01 to 10 parts by mass. A coating agent containing the isocyanate group-containing organosilicon compound according to claim 1. An article coated or surface-treated with the coating agent according to claim 9. A glass fiber product, the surface of which is coated or treated with the coating agent according to claim 9, which is selected from glass cloth, glass tape, glass mat and glass paper. An inorganic filler, the surface of which is coated or treated with the coating agent according to claim 9. A ceramic whose surface is coated or treated with the coating agent according to claim 9. A metal whose surface is coated or treated with the coating agent according to claim 9. An adhesive polarizing plate comprising a polarizing film and an adhesive layer formed from the adhesive according to claim 8 on one side or both sides of the polarizing film. A liquid crystal display device comprising a liquid crystal panel having a liquid crystal cell in which liquid crystal is sealed between a pair of glass substrates, and the pressure-sensitive adhesive polarizing plate according to claim 15 attached to one side or both sides of the liquid crystal cell.

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