JP5729253B2 - Condensation reaction curable silicone release coating composition - Google Patents

Description

  The present invention relates to a condensation reaction curable silicone release coating composition.

  A method for obtaining a material exhibiting releasability to pressure-sensitive adhesive materials such as pressure-sensitive adhesives by forming a releasable cured film on the surface of various substrates such as paper, laminated paper, and plastic film has been known for a long time. . A silicone composition is used as a material for forming such a peelable cured film. For example, Japanese Patent Publication No. 35-13709 (Patent Document 1) and Japanese Patent Publication No. 36-1397 (Patent Document 2) include: A condensation reaction curable silicone release coating composition comprising a silanol group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a tin compound has been proposed.

  Thereafter, when an addition reaction curable composition as disclosed in Japanese Patent Publication No. 46-26798 (Patent Document 3) or the like is developed, the curing property and pot life are better than those of the condensation type. In rare cases, additional types began to spread widely. In particular, in the release paper application that requires a short time curing at a relatively low heating temperature, the addition type continues to be used mainly.

  The tin compound usually used in the condensation reaction curable type is excellent in curability, colorless, liquid, and soluble in silicone. However, the tin compound is mainly used, but has the disadvantage of being toxic. (Reproductive toxicity). In addition, the problem of environmental load as a suspected environmental hormone has been pointed out, and the use of such substances has become more restrictive.

Nevertheless, the condensation reaction curing type has the advantage that it can be used in applications with addition reaction catalyst poisons, and there are many types of other materials that can be mixed and used. If it solves, the use expansion to various uses as a silicone release coating composition is anticipated.
Therefore, non-tin catalyst has been conventionally studied. JP-A-59-176326 (Patent Document 4) discloses a quaternary phosphonium hydroxide compound, WO 2008/081890 (Patent Document 5) discloses a quaternary ammonium ion compound, US Pat. No. 3,719,633. No. (Patent Document 6), US Pat. No. 4,180,462 (Patent Document 7), and Japanese Translation of PCT International Publication No. 2011-506588 (Patent Document 8) propose organic substances such as guanidine. The use of natural minerals such as kaolin is also introduced in 2011-510103 (Patent Document 9).

  As a metal compound, a titanium-based or zinc-based compound has been conventionally used, and recently, an Ir compound is disclosed in JP-T-2007-527932 (Patent Document 10), and JP-A 2010-163602 (Patent Document 11). Zr compound, JP 2011-506638 (patent document 12) Zn compound, JP 2011-506744 (patent document 13) Mo compound, JP 2011-506739 (patent document 14) Cu Proposals have been made on various metals such as Ag, B, Sc, Ce, Bi, Ge, and Mn.

  However, these have a slower reaction rate than a tin-based catalyst, have problems of gelation, a catalyst effect is not obtained so much, and costs are increased, so it cannot be said that they are widely used industrially. . These disadvantages become a major obstacle especially when used in applications as silicone release coatings that require short time curing at relatively low heating temperatures.

Japanese Patent Publication No. 35-13709 Japanese Patent Publication No. 36-1397 Japanese Examined Patent Publication No. 46-26798 JP 59-176326 A International Publication No. 2008/081890 Pamphlet US Pat. No. 3,719,633 US Pat. No. 4,180,462 Special table 2011-506588 gazette Special table 2011-510103 gazette JP-T-2007-527932 JP 2010-163602 A Special table 2011-506738 gazette Special table 2011-506744 gazette Special table 2011-506739 gazette

  The present invention has been made in view of such problems, and is applied to the surface of paper, laminated paper, plastic film, etc., and forms a non-adhesive film excellent in releasability on various substrate surfaces. It is an object of the present invention to provide a dehydrogenation and dealcohol condensation reaction-curable silicone release coating composition that can be used.

  As a result of intensive studies using various materials in order to achieve the above object, the present inventors have conducted dehydrogenation and dehydrogenation by a method using a specific nitrogen atom-containing compound as a co-catalyst with a non-tin metal compound catalyst. It has been found that a composition having excellent performance as a dealcoholization condensation curable silicone release coating agent can be obtained, and the present invention has been made.

上記式中、Ｍｅはメチル基、Ｅｔはエチル基を示す。
［４］
（Ｄ）成分として、上記有機化合物中の酸素原子の一部又は全てが硫黄原子に置き換わった化合物を単独で又はこれと上記有機化合物とを組み合わせて用いる［１］〜［３］のいずれかに記載の組成物。
［５］
（Ｃ）成分の縮合反応触媒が、アルミニウム三価、鉄三価、コバルト三価、亜鉛二価、ジルコニウム四価又はビスマス三価の化合物であって、配位子として有機酸、アルコキシド又はキレート剤を結合した化合物である［１］〜［４］のいずれかに記載の組成物。
［６］
（Ｃ）成分の縮合反応触媒が、アルミニウム三価、鉄三価又はビスマス三価の化合物であって、配位子として有機酸又はキレート剤を結合した化合物である［５］記載の組成物。
［７］
更に、（Ｅ）有機溶剤を含有する［１］〜［６］のいずれかに記載の組成物。
［８］
トルエン１９００質量部に（Ａ）〜（Ｄ）成分を上記配合量範囲内で溶解させたときの２５℃における２４時間経時後の粘度が初期粘度の２倍以下である［１］〜［７］のいずれかに記載の組成物。 That is, the present invention provides the following condensation reaction curable silicone release coating composition.
[1]
(A) Organopolysiloxane containing at least two silanol groups in one molecule
100 parts by mass,
(B) (B-1) 0.1-20 parts by mass of an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) directly bonded to silicon atoms in one molecule, and / or (B-2) 0.1-20 parts by mass of an organopolysiloxane having at least three hydrolyzable groups directly bonded to silicon atoms in one molecule, and an SiH group and a hydrolyzable group which are active groups in the component (B) The amount corresponding to 1 to 200 times the number of moles of the silanol group of component (A),
(C) Condensation reaction catalyst of a compound selected from magnesium, aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, zirconium, tungsten and bismuth
Catalyst amount,
Through 1-3 (D) carbon atoms saw containing a nitrogen atom and an oxygen atom and / or a sulfur atom is bonded structure, organic compounds and two or more reacts of those shown below ii~iv 1 to 20 parts by mass of an organic compound promoter selected from the organic compounds produced
ii. Reaction product of isocyanate group-containing compound and hydroxyl group and / or amino group-containing compound
iii. Ring opening reaction product of amino group-containing compound and epoxy compound
iv. A condensation reaction curable silicone release coating composition comprising a ring-opening reaction product of an amino group-containing compound and an oxetane compound .
[2]
The component (D) has (I) a molecular weight of 10,000 or less, (II) has a substituent containing a silicon atom in the molecule, or has both (I) and (II). The composition according to [1].
[3]
(D) The composition according to [1] or [2], wherein the component is selected from compounds represented by the following formula.

In the above formula, Me represents a methyl group, and Et represents an ethyl group.
[4]
As the component (D) , any one of [1] to [3] wherein a compound in which some or all of the oxygen atoms in the organic compound are replaced with sulfur atoms is used alone or in combination with the organic compound is used . The composition as described.
[5]
The (C) component condensation reaction catalyst is an aluminum trivalent, iron trivalent, cobalt trivalent, zinc divalent, zirconium tetravalent or bismuth trivalent compound, and an organic acid, alkoxide or chelating agent as a ligand. The composition according to any one of [1] to [4], which is a bonded compound.
[6]
The composition according to [5], wherein the condensation reaction catalyst of component (C) is a trivalent aluminum, iron trivalent, or bismuth trivalent compound, and is a compound in which an organic acid or a chelating agent is bound as a ligand.
[7]
Furthermore, (E) The composition in any one of [1]-[6] containing an organic solvent.
[8]
[1] to [7] The viscosity after 24 hours of aging at 25 ° C. when the components (A) to (D) are dissolved in 1900 parts by mass of toluene within the above-mentioned blending amount range is not more than twice the initial viscosity [1] to [7]. The composition in any one of.

According to the present invention, excellent curability and release characteristics can be achieved even when a non-tin metal compound catalyst that is inferior in curability and release characteristics as compared to a tin-based metal compound catalyst is used. In addition, by providing a condensation reaction curable silicone release coating composition that does not contain a tin compound, which has been pointed out as a problem in safety and environmental impact, it can be used for applications that were difficult to apply in the addition reaction curable type. It can be applied to various application methods such as expanded use and mixing with various other materials.
The formed cured film exhibits good adhesion to various substrates. In addition, shelf life and pot life are good, workability is excellent, and stable characteristics can be obtained.

[(A) Organopolysiloxane]
Component (A) is an organopolysiloxane having at least two hydroxy groups bonded directly to silicon atoms in one molecule. The monovalent organic group other than the hydroxy group directly bonded to the silicon atom is not particularly limited. Specific examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cyclopentyl group, and a cyclohexyl group. Examples thereof include cycloalkyl groups such as groups, aryl groups such as phenyl groups and naphthyl groups, and monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkenyl groups such as vinyl groups and propenyls. It is preferable that 80 mol% or more of the organic groups other than is a methyl group. The molecular structure is not particularly limited, but basically a straight chain is industrially preferred, but a branched structure can be used as well.
The absolute viscosity of the 30% by weight toluene solution at 25 ° C. measured by a rotational viscometer of the organopolysiloxane as the component (A) is preferably 50 mPa · s or more, more preferably 50 to 100,000 mPa · s.

Specific examples of the component (A) include organopolysiloxanes represented by the following formulas (1-1) and (1-2). R in the formula is an alkyl group such as a hydroxyl group, a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, an aryl group such as a phenyl group or a naphthyl group, a vinyl group or a propenyl group. In addition to the monovalent hydrocarbon group having 1 to 10 carbon atoms such as the alkenyl group, the siloxane residues of the structural formulas (2-1) and (2-2) (formula (2-1) and formula (2-2) R ¹ therein is an oxygen atom or an alkylene group having 1 to 6 carbon atoms such as a methylene group or an ethylene group, and R is the same as above. α1 is a number from 0 to 1000, in particular from 0 to 900, and β1 is a number from 50 to 9000, in particular from 60 to 9000. α2 is a number from 0 to 900 and β2 is a number from 0 to 9000, but is a number having two or more hydroxyl groups in one molecule.

（上記式中、Ｍｅはメチル基を示す。）

(In the above formula, Me represents a methyl group.)

[(B-1) Organohydrogenpolysiloxane]
The (B-1) organohydrogenpolysiloxane that can be used as the component (B) of the present invention has at least 3, preferably 4 to 1000, hydrogen atoms bonded directly to silicon atoms in one molecule. There is no particular limitation except that it is necessary, and the molecular structure may be linear, branched or cyclic. The absolute viscosity at 25 ° C. of the (B-1) organohydrogenpolysiloxane of the present invention measured at 25 ° C. may be in the range of several mPa · s to tens of thousands mPa · s.
Specific examples of the organohydrogenpolysiloxane include the following.

However, in the above structural formula and compositional formula, Me represents a methyl group, Y and Z are groups represented by the above structural formula, respectively, and a to k and m to q are integers in the following ranges. is there. a, e and g are 3 to 500, particularly 4 to 500, f, i and m are 0 to 500, particularly 0 to 400, b, c, d, h, j, k, n, o, p and q are It is an integer from 0 to 500, in particular from 0 to 400.

[(B-2) Hydrolyzable group-containing organopolysiloxane]
The organopolysiloxane that can be used as the component (B-2) of the present invention has at least 3, preferably 3 to 1000 hydrolyzable groups bonded to silicon atoms in one molecule. Examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and an isopropenoxy group directly bonded to a silicon atom, and an acyloxy group such as an acetoxy group. An amino group such as an ethylamino group, an amide group, an oxime group such as an ethylmethylbutanoxime group, and a halogen atom such as a chlorine atom or a bromine atom may be mixed.

As the hydrolyzable group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are industrially preferable. Specifically, the following organopolysiloxanes can be used. r is a number from 0 to 200, in particular from 0 to 190, and s is from 0 to 1000, in particular from 0 to 900. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

Some of the alkoxy groups are CH ₃ COO—, CH ₃ (C ₂ H ₅ ) C═NO—, (C ₂ H ₅ ) ₂ N—, CH ₃ CO (C ₂ H ₅ ) N—, CH _2. May be substituted with a group such as ═ (CH ₃ ) CO—.

  (B) Component (B-1) The organohydrogenpolysiloxane is blended in such a way that the number of moles of hydrogen atoms bonded to silicon atoms (hereinafter referred to as SiH groups) is the hydroxyl group contained in component (A). Is an amount corresponding to 1 to 200 times, particularly 1 to 190 times the total number of moles. The blending amount of (B-2) organopolysiloxane is such that the number of moles of hydrolyzable groups bonded to silicon atoms is 1 to 200 times, especially 1 to 190 times the total number of moles of hydroxyl groups contained in component (A). The corresponding amount. When the number of moles of the active groups (SiH group and hydrolyzable group) contained in the component (B) is less than the above lower limit, the curability of the coating silicone composition of the present invention becomes insufficient, while the upper limit is exceeded. Even if it mixes, the remarkable effect is not seen, but on the contrary, it causes a change with time and is disadvantageous economically. As a compounding quantity of a general (B) component, it is 0.1-30 mass parts with respect to 100 mass parts of (A) organopolysiloxane, Especially 0.1-29 mass parts is the range. (B) As a component, (B-1) or (B-2) may be used independently, or these may be mixed and used. Moreover, you may use what has both a SiH group and a hydrolysable group in 1 molecule.

[(C) Curing catalyst]
The catalyst as the component (C) used in the composition of the present invention is a condensation reaction curing catalyst used for promoting a so-called crosslinking reaction between the component (A) and the component (B) and forming a cured film. A metal compound selected from magnesium, aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, zirconium, tungsten, and bismuth can be used as the condensation reaction catalyst. Preferred examples include metal compounds such as aluminum trivalent, iron trivalent, cobalt trivalent, zinc divalent, zirconium tetravalent, bismuth trivalent organic acid salts, alkoxides, and chelate compounds. For example, organic acid salts such as octylic acid, lauric acid and stearic acid, alkoxides such as propoxide and butoxide, catechol, crown ether, polyvalent carboxylic acids and hydroxy acids and their conjugates, 1,3-diketones And a chelate compound such as a conjugate base of β-keto acid esters, and a plurality of types of ligands may be bonded to one metal.
In particular, aluminum, iron, and bismuth compounds that are easy to obtain stable curability even if the blending and use conditions are slightly different are preferable.

  The amount of the above-mentioned condensation reaction catalyst used may be a catalytic amount, but it can be used in an amount of 0.1 to 20% by mass as the metal content relative to the component (A), and can be arbitrarily selected depending on the curing conditions.

アロファネート基

等が挙げられ、これらを含む環構造の置換基としては、オキサゾリン、オキサゾール、オキサジンなどの環状イミノエーテル、マレイミド、フタルイミドなどの環状イミド、ピロリドンなどの環状ラクタムなどの構造を持つ基が挙げられる。これらのなかで、イソシアネート基から誘導される化合物がより好ましく用いられる。また、その２量体、３量体、それらから誘導される化合物、水酸基及び／又はアミノ基含有化合物との反応物などが使用される。 [(D) Cocatalyst]
The component (D) of the composition of the present invention is an organic compound having a structure in which a nitrogen atom (N) and an oxygen atom (O) are bonded via 1 to 3 carbon atoms (C). Those having a structure of —O—C—N— bonded through one carbon atom include a cyanate group —O—C≡N, a trimer cyanurate group, an isocyanate group —N═C═O, dimer uretdione groups, trimers isocyanurate group, amide group -CO-NH-, carbamate group -O-CO-NH _2, urethane group -O-CO-NH-, urea groups -NH-CO-NH- ,
Biuret group

Allophanate group

Examples of the substituent of the ring structure containing these include cyclic imino ethers such as oxazoline, oxazole and oxazine, cyclic imides such as maleimide and phthalimide, and groups having a structure such as cyclic lactam such as pyrrolidone. Of these, compounds derived from isocyanate groups are more preferably used. In addition, dimers, trimers, compounds derived therefrom, reaction products with hydroxyl group and / or amino group-containing compounds, and the like are used.

  Examples of the compound having a structure of —O—C—C—N— include compounds derived from ethanolamine. Various compounds having a corresponding structure can be prepared by applying a ring-opening reaction of various amino group-containing compounds and epoxy compounds by applying a method for producing ethanolamine in which an amine and ethylene oxide are reacted.

  A compound derived from 1,3-aminoalcohol is exemplified as one having a structure of —O—C—C—C—N—. Various compounds having a corresponding structure can be prepared by applying a ring-opening reaction of various amino group-containing compounds and oxetane compounds by applying a method for producing 1,3-amino alcohol in which amine and oxetane are reacted.

  (D) As a component, the organic compound which 2 or more types of the said compound reacts and produces | generates can also be used.

  In addition, some or all of the oxygen atoms (O) contained in these compounds may be replaced with sulfur atoms (S), and can be prepared using isothiocyanate, thiacyclopropane, thietane, or the like. .

  As the component (D), any one of a compound having a structure in which a nitrogen atom and an oxygen atom are bonded via a carbon atom, and a compound in which part or all of the oxygen atom in the compound is substituted with a sulfur atom, or Both can be used.

As another feature of the component (D), the silicone composition of the present invention is required to have good solubility. Although it depends on the structure of the compound, the higher the molecular weight, the lower the solubility, and the molecular weight is preferably 10,000 or less, preferably 5000 or less. In the present invention, the molecular weight refers to a number average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: Toluene flow rate: 0.35 mL / min Detector: Differential refractive index detector (RI)
Column: Product name TSKgel-G2000H x 2, G3000H x 1, G4000H x 1, TSKgullcolumn H-L x 1 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (Toluene solution with a concentration of 1% by mass)

In addition, it is desirable to have a substituent containing Si atoms in the molecule because of good solubility. For example ^{_{-SiR 1 m (OR 2) 3}} -m, -O-SiR 1 m (OR 2) 3-m, - (SiR 1 o (OR 2) 2-o -O-) n -SiR 1 m (OR ² ) Examples include silyl groups and siloxane groups represented by _3-m . Here, R ¹ and R ² each have 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a vinyl group, a propenyl group, a butenyl group, and a phenyl group. 10 alkyl groups, allyl groups, and aryl groups, where m = 0 to 3, n = 1 to 10, and o = 0 to 2. These groups may be present in the molecule as polyvalent substituents such as divalent substituents in which some R ¹ and R ² are replaced as bonds.

(D) As a component, it is preferable that it is a thing chosen from the organic compound shown to the following i-iv, and the organic compound which 2 or more types of these react and produce | generate.
i. Isocyanate group-containing compounds and their condensates ii. Reaction product of isocyanate group-containing compound and hydroxyl group and / or amino group-containing compound iii. A ring-opening reaction product of an amino group-containing compound and an epoxy compound iv. Ring opening reaction product of amino group-containing compound and oxetane compound

Specific examples of the component (D) of the present invention include the following. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

  The (D) promoter of the present invention is preferably 1 to 20 parts by mass, more preferably 1 to 19 parts by mass with respect to 100 parts by mass of the component (A). If it is less than this, the curability will be lowered, and if it is too much, the pot life will be insufficient and the workability will be lowered.

[(E) Organic solvent]
The organic solvent of the component (E) of the composition of the present invention is a component blended for the purpose of treatment bath stability, improvement of coating properties for various substrates, adjustment of coating amount and viscosity, such as toluene, An arbitrary amount of an organic solvent capable of uniformly dissolving the composition, such as xylene, ethyl acetate, acetone, methyl ethyl ketone, ethanol, IPA, hexane, heptane, can be used, and 10 to 1900 parts by mass with respect to 100 parts by mass of component (A) Although it can contain, (E) component does not need to be mix | blended depending on the coating method.

[Other ingredients]
If necessary, the composition of the present invention may be blended with known slipperiness imparting agents, adhesion improvers, peel strength control agents, pigments, leveling agents, and bath life extending agents.

The composition of the present invention can be easily produced by uniformly mixing the components (A), (B), (C), (D) and, if necessary, (E). In this mixing, it is advantageous to mix the components (B), (C), and (D) after the component (A) is uniformly dissolved in the component (E).
The composition of the present invention has a feature that the pot life is better than a conventional condensation reaction curable composition by not containing a tin catalyst, but in order to ensure a sufficient pot life, the component (C) is: It is better to add and mix just before coating.

  In the present invention, the pot life of the composition obtained by adding 1900 parts by mass of toluene as the component (E) is not more than twice the initial viscosity measured by a rotational viscometer after 24 hours at 25 ° C. And from the viewpoint of workability.

  When coating using the composition of the present invention, the composition of the present invention is diluted directly or with an appropriate organic solvent, and then coated with a bar coater, roll coater, reverse coater, gravure coater, air knife coater, or thin film. The coating is performed on a substrate such as paper, laminated paper, or plastic film by a known coating method such as a high-precision offset coater or multi-stage roll coater.

The amount of the composition of the present invention applied to the substrate varies depending on the type of material of the substrate to be coated, but is preferably in the range of 0.1 to 5.0 g / m ² as the solid content. By heating the substrate coated with the composition of the present invention as described above at 80 to 180 ° C. for 5 to 60 seconds, a cured film is formed on the surface of the substrate to obtain a desired release paper and release film. it can.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group, and Et represents an ethyl group.

で示される化合物を１０質量部加え、２０〜４０℃で１時間撹拌混合した。 [Example 1]
As component (A), the viscosity of a 30% by weight toluene solution at 25 ° C. measured by a rotational viscometer is 10,000 mPa · s, both ends of the molecular chain are blocked with dimethylhydroxysilyl groups, and the main skeleton is a dimethylsiloxane unit. 100 parts by weight of the organopolysiloxane composed of 1800 parts by weight of toluene as component (E) was dissolved by stirring at 20 to 40 ° C. In the obtained solution, as component (B-1), both ends of the molecular chain are blocked with trimethylsilyl groups, and contain 95 mol% of a unit represented by MeHSiO _2/2 , and the absolute viscosity is 25 mPa · s. 3 parts by mass of a certain methylhydropolysiloxane as component (D),

10 parts by mass of the compound represented by is added, and the mixture is stirred and mixed at 20 to 40 ° C. for 1 hour.

The component (D) was obtained by reacting an equimolar amount of a compound represented by the following formula at 140 ° C. for 6 hours. The main component was a condensate of an epoxy group and an amino group, and the average molecular weight was 400.

Immediately before coating on the substrate, a trivalent bismuth carboxylate was added as a component (C) to a Bi equivalent amount of 3% by mass with respect to the component (A) to prepare a composition.
This is uniformly coated on glassine paper using a Mayer bar and cured under predetermined conditions (150 ° C. for 30 seconds) to produce an evaluation sample having a coating amount of 1.0 g / m ^{2 in} solid content. did. The evaluation was in accordance with the description of the evaluation method for cured film properties below, and the results are shown in Table 1.

[ Reference Example 1 ]
In Example 1, the composition was prepared similarly except having used 10 mass parts of the following compounds as (D) component.

In addition, (D) component obtained the trimer by condensing 3 mol isocyanate groups of the compound shown by a following formula according to a well-known method. The average molecular weight was 600.

[Example 2 ]
In Example 1, the composition was prepared similarly except having used 10 mass parts of the following compounds as (D) component.

In addition, (D) component was obtained by making equimolar the compound shown by a following formula react at 50 degreeC for 6 hours. The main component was a condensation product of an isocyanate group and an amino group, and the average molecular weight was 350.

[Example 3 ]
In Example 1, the composition was prepared similarly except having used 10 mass parts of the following compounds as (D) component.

で示される化合物１モルに、下記式

で示される化合物１モルを１４０℃で６時間反応させた後、下記式

で示される化合物１モルを５０℃で６時間反応させて得た。平均分子量は６００であった。 In addition, (D) component is a following formula

In 1 mol of the compound represented by the formula:

After reacting 1 mol of the compound represented by the formula at 140 ° C. for 6 hours,

It was obtained by reacting 1 mol of the compound represented by the formula at 50 ° C. for 6 hours. The average molecular weight was 600.

[Example 4 ]
In Example 1, the composition was prepared similarly except having used 10 mass parts of the following compounds as (D) component.

で示される化合物１モルに、下記式

で示される化合物２モルを１４０℃で６時間反応させて得た。平均分子量は７００であった。 In addition, (D) component is a following formula

In 1 mol of the compound represented by the formula:

It was obtained by reacting 2 mol of the compound represented by the formula at 140 ° C. for 6 hours. The average molecular weight was 700.

なお、（Ｄ）成分は、下記式

で示される化合物１モルに、下記式

で示される化合物１モルを１４０℃で６時間反応させて得た。平均分子量は４００であった。 [Example 5 ]
In Example 1, the composition was prepared similarly except having used 10 mass parts of the following compounds as (D) component.

In addition, (D) component is a following formula

In 1 mol of the compound represented by the formula:

1 mol of the compound represented by the formula (1) was obtained by reacting at 140 ° C. for 6 hours. The average molecular weight was 400.

[Example 6 ]
In Example 1, it carried out similarly except having used tetraacetyl acetonate iron as a component (C) 3 mass% of Fe conversion amount to (A) component.

[Example 7 ]
In Example 1, as the component (A), the viscosity of a 30% by mass toluene solution at 25 ° C. is 15000 mPa · s, both ends of the molecular chain are blocked with dimethylhydroxysilyl groups, and the main skeleton is 99.9 dimethylsiloxane units. 100 parts by weight of an organopolysiloxane composed of 0.01% by mole of a hydroxymethylsiloxane unit and (B-2) component as a partial hydrolysis-condensation product of MeSi (OMe) ₃ having a viscosity of 10 mPa · It implemented similarly except having changed the methyl methoxy polysiloxane which is s into 5 mass parts.

[Example 8 ]
In Example 7 , it implemented similarly except having made tetraacetylacetonato aluminum into 3 mass% of Al conversion amount to (A) component as (C) component.

[Example 9 ]
In Example 7 , it implemented similarly except having made tetraacetylacetonate iron into 3 mass% of Fe conversion amount with respect to (C) component with respect to (A) component.

[Example 10 ]
In Example 7 , as the component (C), tetraacetylacetonato aluminum was added in an amount of 1.5 mass% in terms of Al, and the component (A) was mixed with a trivalent Bicarboxylate in an amount of 1.5 mass% in terms of Bi. It carried out similarly.

[Example 11 ]
In Example 7 , as the component (C), tetraacetylacetonate iron was added in an amount of 1.5 mass% in terms of Fe, and the component (A) was trivalent bismuth carboxylate in an amount of 1.5 mass% in terms of Bi. It carried out similarly.

[Comparative Example 1]
In Example 1, it carried out similarly except not mix | blending (D) component, and produced the sample for evaluation.

[Comparative Example 2]
In Example 1, the composition was prepared similarly except having mix | blended the following compound as (D) component.

[Comparative Example 3]
In Example 1, the composition was prepared similarly except having mix | blended the following compound as (D) component.

[Comparative Example 4]
In Example 1, it carried out similarly except not mix | blending (D) component and mix | blending 3 mass% of dioctyltin dicarboxylate as a (C) component in tin conversion amount.

[Comparative Example 5]
In Example 7 , it carried out similarly except not mix | blending (D) component and mix | blending dioctyltin dicarboxylate as a (C) component 3 mass% with respect to tin with respect to (A) component.

Evaluation Method of Cured Film Characteristics 1) Curability A catalyst-added silicone composition is applied to PE laminated paper in a solid content of 1.0 g / m ² and heat treated for 30 seconds with a 130 ° C. hot air circulating dryer for 30 seconds. And a sample for evaluation was produced.
The surface of the cured film of the sample was rubbed with a finger, the degree of cloudiness on the surface of the film was observed, and evaluated according to the following criteria.
○: Clouding does not occur when heated at 130 ° C. for 30 seconds.
Δ: Thin and cloudy.
X: Thick cloudiness occurs or is uncured.

2) Adhesiveness The catalyst-added silicone composition was applied to PE-laminated paper at a solid content of 1.0 g / m ² and heat-treated with a hot air circulating dryer at 150 ° C. for 30 seconds to form a cured film for evaluation. A sample was prepared.
After leaving the sample at 25 ° C. and 50% RH × 1 day, the surface of the cured film was rubbed with a finger, the degree of dropout of the film surface was observed, and evaluated according to the following criteria.
○: No dropout.
Δ: Dropout occurs partially.
X: Dropping occurs easily.

3) Releasability 2) Prepare a sample for evaluation in the same manner as in the evaluation of adhesion, and apply an acrylic solvent adhesive [Olivein BPS-5127 (manufactured by Toyo Ink Co., Ltd.)] to the surface of the cured film. Then, heat treatment was performed at 100 ° C. for 3 minutes, and then, a high-quality paper having a basis weight of 64 g / m ² was bonded to the treated surface, followed by one reciprocal pressing with a 2 kg roller, and aged at 25 ° C. for 20 hours. This sample was cut into a width of 5 cm, and a tension tester was used to pull the laminated paper at an angle of 180 ° at a peeling speed of 0.3 m / min, and the force (N) required for peeling was measured. For the measurement, Autograph DCS-500 (manufactured by Shimadzu Corporation) was used.

4) Residual adhesion A polyester tape [Nitto 31B (manufactured by Nitto Denko Corporation)] was bonded to the surface of the cured film of the separator, and after aging at 70 ° C. for 20 hours under a load of 20 gf / cm ² , the tape was It peeled off and affixed on the stainless steel plate. Next, this tape was peeled off at an angle of 180 ° with respect to the stainless steel plate surface at a peeling speed of 0.3 m / min, and the force required for peeling was measured. On the other hand, the above-mentioned polyester tape is bonded to the surface of a Teflon (registered trademark) plate, aged under the same conditions, and the force (N) required to peel the tape is measured in the same manner. % Or more was evaluated as ○, 80 to 89% as Δ, and 79% or less as ×.

5) Pot life After the coating liquids prepared in Examples and Comparative Examples were allowed to stand at 25 ° C. for 1 day, the appearance was observed. Good ones were marked with ◯, and those with thickening, gelation and precipitation were marked with ×.

  If the composition of the present invention is used, a release paper excellent in the properties of the cured film can be produced without using a tin-based catalyst, and the workability is also good because of excellent storage stability.

Claims (8)

(A) Organopolysiloxane containing at least two silanol groups in one molecule
100 parts by mass,
(B) (B-1) 0.1-20 parts by mass of an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) directly bonded to silicon atoms in one molecule, and / or (B-2) 0.1-20 parts by mass of an organopolysiloxane having at least three hydrolyzable groups directly bonded to silicon atoms in one molecule, and an SiH group and a hydrolyzable group which are active groups in the component (B) The amount corresponding to 1 to 200 times the number of moles of the silanol group of component (A),
(C) Condensation reaction catalyst of a compound selected from magnesium, aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, zirconium, tungsten and bismuth
Catalyst amount,
Through 1-3 (D) carbon atoms saw containing a nitrogen atom and an oxygen atom and / or a sulfur atom is bonded structure, organic compounds and two or more reacts of those shown below ii~iv 1 to 20 parts by mass of an organic compound promoter selected from the organic compounds produced
ii. Reaction product of isocyanate group-containing compound and hydroxyl group and / or amino group-containing compound
iii. Ring opening reaction product of amino group-containing compound and epoxy compound
iv. A condensation reaction curable silicone release coating composition comprising a ring-opening reaction product of an amino group-containing compound and an oxetane compound .   The component (D) has (I) a molecular weight of 10,000 or less, (II) has a substituent containing a silicon atom in the molecule, or has both (I) and (II). A composition according to claim 1. The composition according to claim 1 or 2, wherein the component (D) is selected from compounds represented by the following formulae.

In the above formula, Me represents a methyl group, and Et represents an ethyl group. The component (D) according to any one of claims 1 to 3, wherein a compound in which some or all of the oxygen atoms in the organic compound are replaced with sulfur atoms is used alone or in combination with the organic compound. Composition.   The (C) component condensation reaction catalyst is an aluminum trivalent, iron trivalent, cobalt trivalent, zinc divalent, zirconium tetravalent or bismuth trivalent compound, and an organic acid, alkoxide or chelating agent as a ligand. The composition according to any one of claims 1 to 4, which is a bonded compound.   6. The composition according to claim 5, wherein the condensation reaction catalyst of component (C) is a trivalent aluminum, iron trivalent, or bismuth trivalent compound, and is a compound in which an organic acid or a chelating agent is bound as a ligand.   Furthermore, (E) The composition of any one of Claims 1-6 containing the organic solvent.   8. The viscosity after 24 hours of aging at 25 ° C. when the components (A) to (D) are dissolved in 1900 parts by mass of toluene within the above range of blending amount is not more than twice the initial viscosity. A composition according to claim 1.