CN103588930A

CN103588930A - Nitrile group-containing polymer, synthesizing method thereof, composition using nitrile group-containing polymer, and laminated body

Info

Publication number: CN103588930A
Application number: CN201310298307.XA
Authority: CN
Inventors: 加纳丈嘉; 永﨑秀雄; 佐藤真隆
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2006-10-23
Filing date: 2007-10-22
Publication date: 2014-02-19
Anticipated expiration: 2027-10-22
Also published as: CN103588930B

Abstract

A process for producing a metal film-coated material, the process including: (a1) forming, on a substrate, a polymer layer formed from a polymer which has a functional group capable of interacting with a plating catalyst or a precursor thereof, and is directly chemically bonded to the substrate; (a2) providing a plating catalyst or a precursor thereof to the polymer layer; and (a3) performing plating with respect to the plating catalyst or a precursor thereof. The polymer layer satisfies all of the following requirements (1) to (4): (1) the saturated water absorption coefficient of the polymer layer as measured in an environment of temperature of 25 DEG C and relative humidity of 50 % is 0.01 to 10% by mass; (2) the saturated water absorption coefficient of the polymer layer as measured in an environment of temperature of 25 DEG C and relative humidity of 95 % is 0.05 to 20% by mass; (3) the water absorption coefficient of the polymer layer as measured after 1 hour of immersion in boiling water at 100 DEG C is 0.1 to 30% by mass; and (4) the surface contact angle of the polymer layer as measured after dropping 5 [mu]L of distilled water thereonto and leaving to stand for 15 seconds in an environment of temperature of 25 DEG C and relative humidity of 50 % is 50 to 150 degrees.

Description

The composition of the polymkeric substance that the polymkeric substance that contains itrile group and synthetic method thereof, use contain itrile group and layered product

The application be Patent Office of State Intellectual Property Office to national applications number be: 200780039405.4, international application no is that PCT/JP2007/070545, international filing date are the dividing an application of " surface metal mould material and manufacture method thereof, metal pattern material and manufacture method thereof, polymer layer form composition and the layered product of the polymkeric substance that contains itrile group with composition, the polymkeric substance that contains itrile group and synthetic method thereof, use " patent application by name on October 22nd, 2007.

Technical field

The present invention relates to a kind of manufacture method, surface metal mould material of surface metal mould material, manufacture method, metal pattern material and the polymer layer formation composition of metal pattern material.The invention still further relates to novel polymer, its synthetic method, the composition that contains this polymkeric substance that contains itrile group and polymerizable group and the layered product that uses said composition to make.

Background technology

At present, the metal wiring substrate that forms distribution by metal pattern on the surface of insulativity substrate is just being widely used in electronic component or semiconductor element.

As the manufacture method of this metal pattern material, main use " elimination method ".This elimination method refers on the metallic membrane forming on substrate surface and arranges and irradiate and the sensitive layer of sensitization by active ray, this sensitive layer is carried out to image exposure, and then video picture forms resist layer picture, then etching metal film, form metal pattern, finally peel off the method for resist layer.

In the metal pattern being obtained by the method, by design the concavo-convex fixing effect that produces on substrate surface, find the adaptation between substrate and metallic membrane.Therefore, concavo-convex due to the substrate interface part of metal pattern, has the poor problem of high frequency waves characteristic while using as metal wiring.And, for substrate surface is carried out to concavo-convexization processing, must, with strong acid treatment substrate surfaces such as chromic acid, exist in order to obtain the good metal pattern of adaptation of metallic membrane and substrate, the problem that step is numerous and diverse.

In order to address this problem, proposed to carry out Cement Composite Treated by Plasma on the surface of substrate, on substrate surface, introduce polymerization initiating group, from this polymerization initiating group, carry out monomer polymerization, to generate the mode of the surface grafting polymerization thing with polar group at substrate surface, carry out surface treatment, thereby do not make the surface roughening of substrate, improve the adaptation (for example, referring to non-patent literature 1) of substrate and metallic membrane.But, according to the method, because graftomer has polar group, to the variation of temperature or humidity, can produce absorption or the disengaging of moisture, metallic membrane or substrate that result has formation produce the problem of distortion.

And, while using as the distribution of metal wiring substrate as the metal pattern that utilizes the method to obtain, at the remaining graftomer with polar group of substrate interface part, because moisture or ion etc. become, easily keep, have the worry of the resistance to ion transport of temperature humidity dependency or wiring closet or the variation of shape.Especially, in the time of in being applicable to the meticulous distributions such as printing distributing board, between distribution (metal pattern), must keep high insulativity, present situation is that the insulation reliability of wiring closet is had to the requirement further making progress.

Photocurable resin composition is from these good features, not only as the material of above-mentioned surface treatment purposes, also for resist layer material, material for press plate, coating material, light appearance with material etc.In Photocurable resin composition by radical polymerization curing material, generally by tackiness agent, polyfunctional monomer, Photoepolymerizationinitiater initiater, formed.Now, as the method that improves photocuring susceptibility, there is the method for using the tackiness agent with polymerizable group.

On the other hand, finish materials, must have the function of adsorbing plating catalyst especially for the finish materials that forms electroplating film.General, as the adsorptivity group for plating catalyst, known have carboxylic acid group, hydroxyl, ether etc., but because these functional group's wetting abilities are high, easily keep moisture or ion etc., have the worry that the variation of temperature, humidity dependence or the shape of the electroplating film of formation is exerted an influence.

For these, worry, consideration can take into account the method to the adsorptivity of plating catalyst and hydrophobic functional group use cyano group (itrile group).

As thering is such cyano group and the polymkeric substance of polymerizable group, be well known that the synthetic polymkeric substance of anionoid polymerization for use monomer below (for example, referring to patent documentation 1).

CH ₂=C (CN) COOR ¹oOCCH=CH ₂(R ¹for low-grade alkylidene)

In this synthetic method, anionoid polymerization has been done with micro-moisture, has the problem of operational difficulty.

And, for example, in patent documentation 2, recorded following macromole.

[changing 1]

But in above-mentioned macromole, the polymerizable group in polymkeric substance is few, solidified nature (polymerizability) is low, and because the cyano content in polymer molecule is also low, has the worry to the adsorptivity of plating catalyst.

[patent documentation 1] Unexamined Patent 11-106372 communique

[patent documentation 2] JP 2004-176025 communique

2000 No. 20 1481-1494 of [non-patent literature 1] advanced material (Advanced Materials)

Summary of the invention

[problem that invention solves]

The present invention has considered that the shortcoming of above-mentioned prior art proposes.

That is, the invention provides few surface metal mould material and the manufacture method thereof of change that a kind of adaptation of metallic membrane is good, change closing force with humidity.

And, the invention provides a kind of good metal pattern material and the manufacture method thereof of insulation reliability of the non-formation region at metal pattern.

And then, the invention provides and a kind ofly can form the polymer layer formation composition that water-absorbent is low, hydrophobicity is high and then the good polymer layer of the adsorptivity of plating catalyst or its precursor is obtained.

And then, the invention provides a kind of plating catalyst etc. metal is had to sufficient adsorptivity, and then good novel polymer, the composition that uses it and the layered product of polymerizability.

[solving the means of problem]

The present invention is as the manufacture method of the surface metal mould material of the 1st kind, wherein, there is the following step: (a1) on substrate, form polymer layer, this polymer layer forms interactional functional group by having with plating catalyst or its precursor, and forms with the direct chemically combined polymkeric substance of this substrate; (a2) on this polymer layer, give the step of plating catalyst or its precursor; (a3) step of this plating catalyst or its precursor being electroplated, above-mentioned polymer layer meets following all conditions

.

Condition 1: the saturated water absorption under 25 ℃ of-50% relative humidity environment is

quality %

Condition 2: the saturated water absorption under 25 ℃ of-95% relative humidity environment is

quality %

Condition 3: the water-intake rate flooding after 1 hour in 100 ℃ of boiling water is

quality %

Condition 4: under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds is degree

In the present invention, preferred above-mentioned polymer layer meets following all conditions

Condition 1 ': the saturated water absorption under 25 ℃ of-50% relative humidity environment is

quality %

Condition 2 ': the saturated water absorption under 25 ℃ of-95% relative humidity environment is

quality %

Condition 3 ': the saturated water absorption flooding after 1 hour in 100 ℃ of boiling water is

quality %

Condition 4 ': under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds is

degree

And then (a1) of the present invention step preferably has by direct Chemical bond the polymkeric substance that forms interactional functional group and polymerizable group with plating catalyst or its precursor and carries out on substrate.

And, (a1) preferred configuration of step comprises that (a1-1) forms the polymerization trigger layer that contains polymerization starter or have the functional group of energy initiated polymerization on base material, manufacture the step of substrate, and (a1-2) on this polymerization trigger layer directly Chemical bond there is the step that forms the polymkeric substance of interactional functional group and polymerizable group with plating catalyst or its precursor.

In the present invention, above-mentioned have a multipolymer that the polymkeric substance that forms interactional functional group and polymerizable group with plating catalyst or its precursor preferably comprises the unit that unit that following formula (1) represents and following formula (2) represent.

[changing 2]

In above-mentioned formula (1) and formula (2),

represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, X, Y and Z represent respectively singly-bound or replacement or unsubstituted divalent organic group, ester group, amide group or ether, L independently ¹and L ²represent independently respectively to replace or unsubstituted divalent organic group.

And preferred configuration is that to have the weight-average molecular weight that forms the polymkeric substance of interactional functional group and polymerizable group with above-mentioned plating catalyst or its precursor be more than 20000 in the present invention.

The manufacture method of the surface metal mould material of the 2nd kind of the present invention, wherein, has the following step: (a1 ') forms the step of polymer layer on substrate, and this polymer layer is by having cyano group, and forms with the direct chemically combined polymkeric substance of this substrate; (a2) on this polymer layer, give the step of plating catalyst or its precursor, and (a3) this plating catalyst or its precursor are carried out to plating step.

And (a1 ') step preferred configuration is to be undertaken by the polymkeric substance that directly Chemical bond has cyano group and a polymerizable group on substrate.

And then, (a1 ') step preferred configuration comprises that (a1-1 ') forms the polymerization trigger layer that contains polymerization starter or have functional group that can initiated polymerization on base material, manufacture the step of substrate, and on (a1-2 ') this polymerization trigger layer directly Chemical bond there is the step of the polymkeric substance of cyano group and polymerizable group.

In addition, preferred configuration is that the weight-average molecular weight with the polymkeric substance of above-mentioned cyano group and polymerizable group is more than 20000.

In the present invention, preferably in (a3) step, carry out electroless plating, more preferably after this electroless plating, electroplate again.

And the plating catalyst using in (a2) step in the present invention is preferably palladium.

The manufacture method of the surface metal mould material of the 3rd of the present invention, wherein, there is the following step: (a1 ") forms the step of polymer layer to the two sides of resin film; this polymer layer forms interactional functional group by having with plating catalyst or its precursor; and form with the direct chemically combined polymkeric substance of this substrate; and (a2) on this polymer layer, give the step of plating catalyst or its precursor; and the step of (a3) this plating catalyst or its precursor being electroplated, above-mentioned polymer layer meets following all conditions

quality %

quality %

Condition 3: the water-intake rate flooding after 1 hour in 100 ℃ of boiling water is quality %

Condition 4: under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds is

degree

In other words, according to the manufacture method of the surface metal mould material of the 3rd kind of the present invention, by (a1 ") step, be used as the resin film of substrate; on its two sides, form polymer layer; and then carry out (a2) step and (a3) step, can obtain the surface metal mould material that forms metallic membrane on two sides.

In addition, above-mentioned (a1 ") step, above-mentioned (a2) step and above-mentioned (a3) step preferably, in each step, are carried out the two sides of above-mentioned resin film simultaneously.

Surface metal mould material of the present invention is that the manufacture method by surface metal mould material of the present invention obtains.

And the polymer layer formation composition of the 1st kind of the present invention, wherein, contains the polymkeric substance with cyano group and polymerizable group and the solvent that can dissolve this polymkeric substance, for the manufacture method of surface metal mould material of the present invention.

The polymer layer formation composition of the 2nd kind of the present invention, wherein, contains have-O-(CH ₂) _n(n is-O-

integer) structure that represents and the polymkeric substance of polymerizable group, and can dissolve the solvent of this polymkeric substance, for the manufacture method of surface metal mould material of the present invention.

The manufacture method of metal pattern material of the present invention, wherein, the electroplating film (a4) with the surface metal mould material that the manufacture method by surface metal mould material of the present invention obtains is etched into the step of pattern-like.

That is to say, after the manufacture method of metal pattern material is (a1), (a2) in the manufacture method of carrying out aforesaid surface metal mould material, (a3) step, the electroplating film that makes to form is etched into the step ((a4) step) of pattern-like.

And metal pattern material of the present invention is that the manufacture method by metal pattern material of the present invention obtains.

And, polymkeric substance provided by the invention, wherein, the unit that the unit that contains following formula (1) expression and following formula (2) represent.

[changing 3]

In formula (1) and formula (2),

represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, X, Y and Z represent respectively singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether, L independently ¹and L ²represent independently respectively to replace or unsubstituted divalent organic group.

In polymkeric substance of the present invention, the unit that the preferred following formula in unit (3) that above-mentioned formula (1) represents represents.

[changing 4]

In formula (3), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, Z represents singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether, and W represents that (R represents hydrogen atom or alkyl for Sauerstoffatom or N R.), L ¹represent to replace or unsubstituted divalent organic group.

And then, as polymkeric substance of the present invention, the unit that the preferred following formula in unit (4) that above-mentioned formula (3) represents represents.

[changing 5]

In formula (4), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, V and W represent that respectively (R represents hydrogen atom or alkyl for Sauerstoffatom or N R independently.), L ¹represent to replace or unsubstituted divalent organic group.

In above-mentioned formula (4), preferably W is Sauerstoffatom.

And, preferred L in above-mentioned formula (1), formula (3) or formula (4) ¹for thering is the divalent organic group of amino-formate bond or urea key.

And then, more preferably L in above-mentioned formula (1), formula (3) or formula (4) ¹for total carbon atom number is

9 divalent organic group.

In polymkeric substance of the present invention, the unit that the preferred following formula in unit (5) that above-mentioned formula (2) represents represents.

[changing 6]

In formula (5), R ⁵represent hydrogen atom or replacement or unsubstituted alkyl, U represent Sauerstoffatom or N R ' (R ' represent hydrogen atom or alkyl.), L ²represent to replace or unsubstituted divalent organic group.

L in above-mentioned formula (5) ²in the bond sites with cyano group be preferably there is straight chain, the divalent organic group of branching or cyclic alkylidene, the divalent organic group in the bond sites with this cyano group with straight chain, branching or cyclic alkylidene more preferably total carbon atom number is

And, L in above-mentioned formula (5) ⁵in preferably there is the divalent organic group of aromatic group with the bond sites of cyano group, with the divalent organic group in the bond sites of this cyano group with aromatic base family group more preferably total carbon atom number be

In novel polymer of the present invention, L in preferred above-mentioned formula (1), formula (3) or formula (4) ¹for thering is the divalent organic group of amino-formate bond.

And this novel polymer preferable weight-average molecular weight is more than 20,000.

In novel polymer of the present invention, L in above-mentioned formula (1), formula (3) or formula (4) ¹for thering is the synthetic method (synthetic method of polymkeric substance of the present invention) of polymkeric substance of the divalent organic group of amino-formate bond, describe.

The synthetic method of polymkeric substance of the present invention, wherein, at least, in solvent, is used on side chain and has the polymkeric substance of hydroxyl, and have the compound of isocyanate group and polymerizable group, by this isocyanate group of addition on this hydroxyl, forms L ¹in amino-formate bond.

In the synthetic method of polymkeric substance of the present invention, the polymkeric substance on side chain with hydroxyl is preferably used according to following step

(methyl) acrylate that contains hydroxyl of obtaining of order synthesize.

(1) by (methyl) acrylate that contains hydroxyl and when synthetic (methyl) acrylate that this contains hydroxyl 2 functional acrylates' of by-product mixture be dissolved in water in step

(2) in the aqueous solution obtaining, add after the 1st kind of organic solvent separated with water the step of the separated layer that contains the 1st kind of organic solvent and above-mentioned 2 functional acrylates from water layer

(3) in above-mentioned water layer, dissolve the step of the compound higher than above-mentioned (methyl) acrylate water-soluble that contains hydroxyl

(4) in above-mentioned water layer, add the 2nd kind of organic solvent, extract after above-mentioned (methyl) acrylate that contains hydroxyl concentrated step

And then, according to above-mentioned steps

the isolate that comprises (methyl) acrylate that contains hydroxyl that obtains of order, preferably in its total mass, more than containing 0 quality %, above-mentioned 2 functional acrylates of the following scope of 0.10 quality %.

And in the synthetic method of polymkeric substance of the present invention, the preferred SP value of the solvent of use (Gen Ju Red Tianjin method is calculated) be

more preferably ester series solvent, is more preferably diacetate esters series solvent.

Composition of the present invention, wherein, contains polymkeric substance of the present invention, and ketone series solvent or nitrile series solvent, and particularly, preferably the concentration of the polymkeric substance in said composition is 2 quality %

quality %.

And layered product of the present invention wherein, is coated with composition of the present invention and forms on resin base material.

[effect of invention]

According to the present invention, can provide the adaptation of metallic membrane good, with humidity variation bounding force, change little surface metal mould material and manufacture method thereof.

And, according to the present invention, can provide in the non-formation region insulation reliability of metal pattern good metal pattern material and manufacture method thereof.

Also have, according to the present invention, can provide and form the polymer layer formation composition that water-absorbent is low, hydrophobicity is high and then the good polymer layer of the adsorptivity of plating catalyst or its precursor is obtained.

And then, according to the present invention, can provide the metal of plating catalyst etc. is had to sufficient adsorptivity, and then also good novel polymer, its synthetic method, the composition that uses this novel polymer and layered product of polymerizability.

[optimal morphology carrying out an invention]

Explain the present invention below.

The manufacture method of the manufacture method of surface metal mould material, metal pattern material

The manufacture method of the 1st kind of substrate with metallic membrane of the present invention, wherein, there is the following step: the step that (a1) forms polymer layer on substrate, this polymer layer forms interactional functional group by having with plating catalyst or its precursor, and forms with the direct chemically combined polymkeric substance of this substrate; (a2) step of giving plating catalyst or its precursor on this polymer layer; (a3) step of this plating catalyst or its precursor being electroplated, above-mentioned polymer layer meets all following conditions

quality %

quality %

quality %

degree

And, the manufacture method of the surface metal mould material of the 2nd kind of the present invention, wherein, has the following step: (a1 ') forms the step of polymer layer on substrate, this polymer layer is by having cyano group, and forms with the direct chemically combined polymkeric substance of this substrate; (a2) at this polymer layer, give the step of plating catalyst or its precursor, and the step of (a3) this plating catalyst or its precursor being electroplated.

That is to say, the manufacture method of metal pattern material is in the manufacture method of above-mentioned surface metal mould material, to carry out (a1) or (a1 '), (a2),, (a3) after step, carry out the electroplating film of formation to be etched into the step ((a4) step) of pattern-like.

In the manufacture method of the 1st kind of surface metal mould material of the present invention and the manufacture method of metal pattern material, even if it is low in hot and humid lower water-absorbent to meet the polymer layer of above-mentioned 4 conditions, and hydrophobicity is high.And the polymer layer forming by the manufacture method of the 2nd kind of surface metal mould material of the present invention also water-absorbent under hot and humid is low, and hydrophobicity is high.

And, on substrate, combine and on the polymer layer that polymkeric substance forms, give after plating catalyst etc., use it to electroplate, can obtain and metallic membrane that polymer layer adaptation is good.

According to this point, the surface metal mould material of acquisition is because have the metallic membrane good with substrate adaptation, and then polymer layer do not change with humidity, thereby the bounding force changing with humidity variation is little.Such surface metal mould material is applicable in manufacture method of metal pattern material described later etc., except as electrical harnesses with materials'use, can be used for anti electromagnetic wave film, shielding material etc.

And, so long as the manufacture method of metal pattern material, (a4) step is etched into pattern-like by the electroplating film forming on the whole surface of substrate, obtain metal pattern, even expose under the state of this polymer layer in the non-formation region of this metal pattern, this exposed portions serve does not absorb water, and can not cause the reduction of insulativity.As a result, the metal pattern material forming in the manufacture method of metal pattern material of the present invention is good at the insulation reliability in the non-formation region of metal pattern.

Below, illustrate in the manufacture method of the 1st kind of surface metal mould material of the present invention

each condition.

Condition

middle saturated water absorption and water-intake rate can be measured in the following method.

First, in pressure Reduction Dryer, place substrate, remove after the moisture that substrate contains, condition 1,2 o'clock, in the constant temperature and humidity cabinet of setting preferred temperature and humidity, place, during condition 3, in the water-bath that adds 100 ℃ of boiling water, flood 1 hour, according to quality measurement, change to measure saturated water absorption and water-intake rate.When here, the saturated water absorption in condition 1,2 changes after 24 hours by quality, water-intake rate does not represent.In addition, for forming the layered product of polymer layer on the known aforesaid substrate of quality change in advance, by saturated water absorption and the water-intake rate of same time-and-motion study layered product, according to the difference of the water-intake rate of the water-intake rate of substrate and layered product, can measure the water-intake rate of polymer layer.And, on substrate, do not give polymer layer, use saucer etc., manufacture the monofilm of the polymkeric substance that forms polymer layer, the polymkeric substance monofilm of acquisition is measured to direct water-intake rate by aforesaid method.

Contact angle in condition 4 can be measured by method below.

First, prepare to form the layered product of polymer layer on substrate, keeping in relative humidity is set in the constant temperature and humidity cabinet of 25 ℃-50%.The sample of keeping is placed in the measuring cell of regulation of relative humidity to 25 ℃-50%, use surface contact angle determinator (trade(brand)name: OCA20, Dataphysic s company manufacture), at substrate (polymer layer), above with syringe, make under the distilled water automatic drip of 5 μ L, by CCD photographic camera, by the image input computer of substrate section direction, by image analysis calculation substrate (polymer layer), go up the numerical value of the contact angle of water droplet.

And in the present invention, the polymer layer (a1) obtaining in step preferably meets all following conditions

quality %

quality %

Condition 3 ': the water-intake rate flooding after 1 hour in 100 ℃ of boil water is

quality %

degree

Here, in order to obtain, meet above-mentioned all conditions

(preferably

) polymer layer, as the polymkeric substance that forms this polymer layer, can there are material that water-absorbent is low or the method for hydrophobic material (material that wetting ability is low) used, or in polymer layer, add and reduce absorptive material or add the method that improves hydrophobic material, and then, after polymer layer forms, dipping in the solution of the reactive materials that comprises the polymer molecule hydrophobization that makes to form this polymer layer etc., polymkeric substance is reacted and the methods such as hydrophobization with this reactive materials, calm water-absorbent easy to control or hydrophobic viewpoint are considered, as the polymkeric substance that forms polymer layer, the preferred method of using the material that water-absorbent is low or thering is hydrophobic material (material that wetting ability is low).

First, illustrate in the manufacture method of the 1st kind of surface metal mould material of the present invention

in the manufacture method of each step and the 2nd kind of surface metal mould material of the present invention

each step.

(a1) step

In the manufacture method of the 1st kind of surface metal mould material of the present invention in (a1) step, on substrate, form the step of the polymer layer forming with the direct chemically combined polymkeric substance of this substrate, this polymkeric substance has with plating catalyst or its precursor and forms interactional functional group (only having the situation that is called " interaction group " below).

This polymer layer need to meet above-mentioned condition simultaneously

(a1) step preferably by substrate directly Chemical bond have and form with plating catalyst or its precursor that the polymkeric substance of interactional functional group and polymerizable group carries out.

And, (a1) step preferably includes: (a1-1) on base material, form the step that the polymerization trigger layer contain polymerization starter or to have a functional group that can initiated polymerization is manufactured substrate, and (a1-2) on this polymerization trigger layer, form the step of the polymer layer that has interaction group and form with the direct chemically combined polymkeric substance of this polymerization trigger layer.

And, above-mentioned (a1-2) step preferably has after the polymkeric substance of polymerizable group and interaction group on above-mentioned polymerization trigger layer by contact, give energy, the step of (the whole surface of polymerization trigger layer) upper direct this polymkeric substance of Chemical bond on the whole surface of aforesaid substrate.

Surface grafting

On substrate, in the formation of polymer layer, general use is called the method for surface grafting polymerization.Graft polymerization refers on macromolecular compound chain gives spike, the further polymerization of other monomers of initiated polymerization thus, the method for synthetic graftomer.Particularly, while giving the macromolecular compound formation solid surface of spike, be called surface grafting polymerization.

As surface grafting polymerization method applicable in the present invention, can use any of known method that document records.For example in new polymer experiment, learn 10, polymer association compiles, 1994, vertically altogether recorded photo-grafting polymerization, the plasma irradiating graft polymerization method as surface grafting polymerization method in publishing company limited's distribution, p135.And, in adsorption technology brief guide ,NTS company limited, bamboo, in supervision, distribution in February, 1999, p203, p695, recorded γ line, electron rays isoradial irradiation graft polymerization method.

As the object lesson of photo-grafting polymerization, can there are the method that JP 63-92658 communique, Unexamined Patent 10-296895 communique and Unexamined Patent 11-119413 communique are recorded.

While forming polymer layer in the manufacture method of surface metal mould material of the present invention, except above-mentioned surface grafting method, also can be useful on the end of macromolecular compound chain and give trialkoxysilyl, isocyanate group, cyano group, hydroxyl, carboxyl isoreactivity functional group, the method that it is combined with the linked reaction of the functional group that substrate surface exists.

In these methods, from generating the viewpoint of more graftomer, consider that preferred light graft polymerization method particularly preferably forms polymer layer by the photo-grafting polymerization of UV light.

Substrate

" substrate " in the manufacture method of surface metal mould material of the present invention refers to that its surface is to have the material that polymkeric substance can form the function of direct chemical binding state, this polymkeric substance has with plating catalyst or its precursor and forms interactional functional group, base material itself not only has that the substrate of such surface property forms, and the middle layer (for example polymerization trigger layer described later) of another approach is set on base material, and this middle layer has such characteristic and the substrate that forms is also passable.

Base material, substrate

The stable plate object of base material preferred size using in the present invention, its example includes paper, plastics (polyethylene for example, polypropylene, polystyrene etc.) lamination paper, metal sheet (aluminium for example, zinc, copper etc.), plastics film (Cellulose diacetate for example, cellulosetri-acetate, cellulose propionate, butyric acid Mierocrystalline cellulose, cellulose acetate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide, epoxy, bimaleimide resin, polyphenylene oxide, liquid crystalline polymers, tetrafluoroethylene etc.), the paper of the above-mentioned such metal of lamination or evaporation or plastics film etc.As the base material using in the present invention, preferred epoxy or polyimide resin.

Also have, when these substrate surfaces have polymkeric substance and can form the function of direct chemical binding state, described polymkeric substance has with plating catalyst or its precursor and forms interactional functional group, and this base material itself can be used as substrate.

Substrate in the present invention can use the paragraph numbering of JP 2005-281350 communique

being included in of middle record has the base material that polymerization causes the polyimide at position in skeleton.

And the metal pattern material that the manufacture method by metal pattern material of the present invention obtains can be applicable in semiconductor packages, various electrical harnesses substrates etc.While being used for such purposes, as follows, preferably use the substrate that contains insulative resin.Concrete, preferably use the substrate that insulative resin forms or on base material, there is the substrate of the layer that insulative resin forms.

Obtain the substrate that insulative resin forms, during layer that insulative resin forms, use known insulating resin composition.This insulating resin composition adds the resin as principal constituent, can be combined with various additives according to object.For example, in order to improve the intensity of insulation layer, add polyfunctional acrylate monomer, for improve insulator layer intensity, improve electrical characteristic, add the various means such as inorganic or organic filler.

In addition, " insulative resin " in the present invention refers to the resin can in known insulating film or insulation layer with insulativity that can usage degree, even if be not isolator completely, and can be for the present invention if there is the resin of corresponding object insulativity.

Insulative resin can be thermosetting resin, can be thermoplastic resin, can also be their mixture.Concrete, for example, as thermosetting resin, can there are epoxy resin, phenolic resin, polyimide resin, vibrin, bimaleimide resin, polyolefin-based resins, isocyanate-based resin etc.

As epoxy resin, such as cresol-novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolac type epoxy resin, alkylbenzene phenolic aldehyde type epoxy resin, xenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, phenol with there is the epoxide, triglycidyl group isocyanuric acid ester, alicyclic epoxy resin etc. of condenses of the aromatic aldehyde of phenolic hydroxyl group.They can use separately, also can two or more be combined with.Thus, obtain the good products such as thermotolerance.

As polyolefin-based resins, such as there are multipolymer of polyethylene, vinylbenzene, polypropylene, polyisobutene, polyhutadiene, polyisoprene, cyclic olefine resin, these resins etc.

As thermoplastic resin, such as there are phenoxy resin, polyethersulfone, polysulfones, polyhenylene sulfone, polyhenylene thioether, polyphenylene oxide, polyetherimide etc.

As other thermoplastic resins, can there are 1, two (vinyl penylene) ethane resin (1 of 2-, 2-Bis (vinylphenyl) ethane) or the modified resin of it and polyhenylene ether resin (a day plumage realize wait people, Journal of Applied Polymer Science Vol.92, record in 1252-1258 (2004)), liquid-crystalline polymer (concrete is ベ Network スタ mono-(Bie Kusita) etc. of Network ラレ (Ku Lalei) manufacture), fluoro-resin (PTFE) etc.

Thermoplastic resin and thermosetting resin can be distinguished use separately, also can two or more be combined with.It is by making up shortcoming separately and finding that the object of good effect carries out.Such as because the thermoplastic resin such as polyhenylene ether (PP E) is low to hot tolerance, can carry out and the alloying such as thermosetting resin.For example, use the alloying of PPE and epoxy, triallyl isocyanate or introduce the PPE resin of polymerizability functional group and other thermosetting resin alloying.And isocyanic ester is all good resins of Thermocurable and dielectric properties, its situation about using is separately few, and epoxy resin, maleimide resin, thermoplastic resin etc. are used as modified resin.Detailed content about these, is documented in No. 2002/9, " electronic technology " the 35th page.And, in order to improve dielectric properties, as thermosetting resin, use the product that contains epoxy resin and/or phenolic resin, as thermoplastic resin, use the product that contains phenoxy resin and/or polyethersulfone (PES).

In insulating resin composition, have the compound of the two keys of polymerizability in order to be cross-linked, concrete can contain acrylate, methacrylate compound, is particularly preferably polyfunctional goods.In addition, as the compound with two keys of polymerizability, can use thermosetting resin or thermoplastic resin, such as using methacrylic acid or vinylformic acid etc. in epoxy resin, phenolic resin, polyimide resin, polyolefin resin, fluoro-resin etc., also can use the part of resin to carry out the resin that (methyl) acrylated is reacted.

In insulating resin composition in the present invention, the characteristics such as the physical strength of filming for fortified resin, thermotolerance, weathering resistance, flame retardant resistance, water tolerance, electrical characteristic, can be used the mixture (matrix material) of resin and other compositions.As the material for Composite, can there are paper, glass fibre, silicon dioxide granule, phenolic resin, polyimide resin, bismaleimide-triazine resin, fluoro-resin, polyphenylene oxide resin etc.

And then, in this insulating resin composition, may be combined in as required the weighting agent using in resin material for general wiring board, one or two or more kinds of the organic fillers such as mineral fillers such as silicon-dioxide, aluminum oxide, clay, talcum, aluminium hydroxide, calcium carbonate, cured epoxy resin, crosslinked benzo guanamine resin, crosslinked acrylic acid polymer.Wherein, as packing material, preferably use silicon-dioxide.

And, and then, in this insulating resin composition, can also can add as required one or two or more kinds of the various additives such as tinting material, fire retardant, binding property imparting agent, silane coupling agent, oxidation inhibitor, UV light absorber.

While adding these materials in insulating resin composition, any with respect to resin, preferably exist

the scope of quality % is added, and more preferably exists

the scope of quality % is added.This addition during less than 1 quality %, does not have the strengthening effect of above-mentioned characteristic, and while surpassing 200 quality %, the characteristics such as the distinctive intensity of resin reduce.

Substrate during as purposes for such, the specific inductivity (than specific inductivity) under concrete preferred 1GHz is the substrate that the insulative resin below 3.5 forms, or on base material, has the substrate of the layer that this insulative resin forms.And preferably dielectric loss tangent is the substrate that the insulative resin below 0.01 forms under 1GHz, or on base material, there is the substrate of the layer of this insulative resin formation.

The specific inductivity of insulative resin and dielectric loss tangent can be measured by ordinary method.For example, based on " the 18th time electronics is installed association's lecture conference and taken point set ",, the method for the 189th page of record in 2004, use empty syntonizer perturbation method (for example ε r, tan δ tester, the manufacture of キ mono-コ system (triumphant wealthy nurse) company limited very thin films for) to measure.

Like this, in the present invention, from specific conductivity or dielectric dissipation factor, consider, it is also useful selecting dielectric resin material.As specific inductivity, be below 3.5, dielectric loss tangent is the insulative resin below 0.01, can there are liquid crystalline polymers, polyimide resin, fluoro-resin, polyhenylene ether resin, cyanate ester resin, two (biphenylene) ethane resin etc., also has the modified resin that contains them.

The substrate using in the present invention is considered the purposes in semiconductor packages, various electrical harnesses substrates etc., and preferred surface is concavo-convex is below 500nm, more preferably, below 100nm, is further preferably below 50nm, most preferably is below 20nm.The concave-convex surface of this substrate (being the concave-convex surface of this layer when middle layer or polymerization trigger layer are set) is less, and the metal pattern material of acquisition is during for distribution etc., and the electric losses when high frequency waves power transmission is fewer, is preferred.

In the present invention, substrate is plate object, be for example resin film (plastics film), on its two sides, implement (a1) step, can on the two sides of resin film, form polymer layer (in the manufacture method of the 3rd kind of surface metal mould material of the present invention (a1 ") step).

While forming polymer layer like this on the two sides of resin film (substrate), and then carry out (a2) described later step and (a3) step, can obtain the surface metal mould material that forms metallic membrane on two sides.

In the present invention, spike is given in use on substrate surface, while having made the surface grafting polymerization method of dot generation graftomer with it, when graftomer generates, the functional group of containing polymerization starter or have energy initiated polymerization on base material, to form polymerization trigger layer, is preferably used such substrate.Use this substrate, can produce efficiently active site, generate more graftomer.

Below, the polymerization trigger layer in the present invention is described.In addition, base material is plate object, can form polymerization trigger layer on its two sides.

Polymerization trigger layer

As polymerization trigger layer of the present invention, can there are the layer that contains macromolecular compound and polymerization starter, or the layer that contains polymerizable compound and polymerization starter, there is the layer of functional group that can initiated polymerization.

Polymerization trigger layer of the present invention can dissolve necessary composition in the solvent that can dissolve, and by methods such as coatings, is arranged on substrate surface, by heating or rayed, becomes dura mater to form.

As the compound using in polymerization trigger layer of the present invention, and the adaptation of base material is good, and irradiates homenergic by giving active ray, if can produce the compound of spike, can use without particular limitation.Concrete, can use polyfunctional monomer or in molecule, there is the hydrophobic polymer of polymerizable group and the goods that polymerization starter mixes.

As have the hydrophobic polymer of polymerizable group in such molecule, concrete can there are the homopolymer that the diolefin series homopolymer such as polyhutadiene, polyisoprene, polyprene, (methyl) vinylformic acid allyl ester, methacrylic acid 2-allyl group oxygen base ethyl ester etc. contain allyl monomer;

Diene monomers such as divinyl, isoprene, pentadiene or contain allylic monomer as structural unit, binary or the multiple copolymer of vinylbenzene, (methyl) acrylate, (methyl) vinyl cyanide etc.;

In unsaturated polyester, unsaturated polyester epoxide, unsaturated polyester acid amides, unsaturated polyester vinylformic acid, high density polyethylene(HDPE) equimolecular, there is the wire polymer of carbon-to-carbon double bond or three-dimensional high score subclass etc.

In addition, in this specification sheets, refer to " propenyl, methylpropenyl " both or when one of any, with " (methyl) propenyl ", represent.

The content of these polymerizable compounds is preferably with solid component meter in polymerizability layer

the scope of quality %, particularly preferably

the scope of quality %.

In polymerization trigger layer, contain by giving energy and occur that polymerization causes the polymerization starter of energy.Polymerization starter used herein be by irradiation, the heating of energy such as the active ray of regulation, the irradiation of electron rays etc. can occur polymerization cause can known thermal polymerization, Photoepolymerizationinitiater initiater etc., can be according to the suitable choice for use of object.Wherein, utilize photopolymerization to consider to be applicable to from convenient manufacture, therefore preferably use Photoepolymerizationinitiater initiater.

Photoepolymerizationinitiater initiater is so long as have activity to the active ray irradiating, product from the polymerization trigger layer energy surface grafting polymerization that contains it, be not particularly limited, such as using radical polymerization initiator, anionic polymerization initiator, cationic polymerization initiators etc., but from processing ease, reactive consideration, preferred radical polymerization initiator, cationic polymerization initiators, more preferably radical polymerization initiator.

As such Photoepolymerizationinitiater initiater, concrete for example can there are tertiary butyl Trichloroacetophenon, 2,2 '-diethoxy acetophenone, the such acetophenones of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; Benzophenone (the ketone of 4,4 '-bis-dimethylamino benzophenone, CTX, 2-methyl thioxanthone, 2-ethyl thioxanthone, ITX and so on; The st-yrax ethers of st-yrax, benzoin methyl ether, benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether and so on; The benzyl ketals class of benzyl dimethyl ketal, hydroxycyclohexylphenylketone and so on; The salt compounded of iodine such as the sulfonium salts such as triphenylsulfonium muriate, triphenylsulfonium five hexafluorophosphoric acid esters, phenylbenzene iodine muriate, phenylbenzene iodosulfate etc.

The content of polymerization starter is preferably with solid component meter in polymerization trigger layer

the scope of quality %, particularly preferably

the scope of quality %.

The solvent using while being coated with above-mentioned polymerizable compound and polymerization starter so long as can dissolve the solvent of these compositions, is not particularly limited.From dry easiness, operability, consider, the preferred not too high solvent of boiling point, concrete can select boiling point the solvent of left and right.

Concrete can there are acetone, methylethylketone, hexanaphthene, vinyl acetic monomer, tetrahydrofuran (THF), toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Acetyl Acetone, pimelinketone, methyl alcohol, ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy propyl yl acetate etc.

These solvents can be used alone or as a mixture.In coating solution, the concentration of solids component is

quality % is suitable.

Glue spread while forming polymerization trigger layer on base material causes and can and maintain film-forming properties, prevents that the viewpoint that film is peeled off from considering from giving full play to polymerization, and dried quality optimization is

more preferably

more preferably

In the present invention, as mentioned above, by the method such as be coated with on base material, configure the composition that above-mentioned polymerization trigger layer forms use, and by carrying out film forming except desolventizing, form polymerization trigger layer, but now preferably heat and/or rayed is carried out cured film.Particularly, after heat drying, carry out rayed, the words of rayed preparation cured film, because polymerizable compound in advance solidifying to a certain degree, so can effectively be suppressed at and on polymerization trigger layer, generate the situation that the polymerization trigger layer after graftomer comes off, because of but preferred.

Acid extraction is selected according to the fully dry condition needing of coating solvent, from being applicable to manufacturing, considers, preferably temperature is below 100 ℃, and be in 30 minutes time of drying, and more preferably drying temperature is

time of drying be 10 minutes with the heating condition of interior scope.

The rayed of carrying out as required after heat drying can be used the light source using in the formation reaction of graftomer described later.At the graftomer then carrying out, generate in step, never hinder the active site of polymerization trigger layer and the generation of graftomer of giving power generation to consider, even radical polymerization when the polymerization starter existing in polymerization trigger layer solidifies polymerizable compound, also be under the degree that can not be completely consumed, to carry out rayed, because of but preferred.The rayed time is according to the intensity of light source and difference, but is generally preferably in 30 minutes.As the curing target of such preparation, can there are with the film survival rate after solvent cleaning is below 80%, and the initiator survival rate preparing after solidifying is more than 1%.

And, except the polymerization trigger layer that contains above-mentioned polymerizable compound and polymerization starter, the polymerization trigger layer of preferably recording in JP 2004-161995 communique, this polymerization trigger layer is used polymerization initiating group to be attached to the polymkeric substance on side chain.This polymkeric substance is concrete be on side chain, have polymerization cause can functional group's (polymerization initiating radical) and have bridging property base polymkeric substance (below be called polymerization initiated polymerization thing.), by this polymkeric substance, on polymer chain, there is the polymerization initiating radical of combination, and this polymer chain is by the immobilized form of crosslinking reaction, to form polymerization trigger layer.

The polymerization trigger layer forming so is also suitable as the application's polymerization trigger layer.

Polymerization initiated polymerization thing used herein can there are the paragraph numbering of JP 2004-161995 communique

the polymkeric substance of middle record.The particularly preferred object lesson of polymerization initiated polymerization thing is listed below.

[changing 7]

[changing 8]

The film forming of polymerization trigger layer

The polymerization trigger layer that uses polymerization initiated polymerization thing to form in the present invention is in suitable solvent, to dissolve above-mentioned polymerization initiated polymerization thing, prepares coating fluid, on base material, by coating, waits this coating fluid of configuration, except desolventizing, carries out crosslinking reaction and carrys out film forming.That is to say, by carrying out this crosslinking reaction, make the immobilization of polymerization initiated polymerization thing.By in the immobilization of this crosslinking reaction, preferably use the method for the self-condensation reaction of polymerization initiated polymerization thing, and be combined with the method for linking agent, use linking agent.The example of method as using the self-condensation reaction of polymerization initiated polymerization thing, at bridging property base be-during NCO, have utilization by heating, to carry out the method for the character of self-condensation reaction.By carrying out this self-condensation reaction, can form crosslinking structure.

And, as being combined with the linking agent using in the method for linking agent, can use the current known linking agent of believing record in two volumes " linking agent handbook " under mountain.

As the crosslinkable groups in polymerization initiated polymerization thing and the preferably combination of linking agent, can there are (bridging property base, linking agent)=(COOH, polyamine), (COOH, polynary ethyleneimine), (COOH, multicomponent isocyanate), (COOH, polynary epoxy), (NH ₂, multicomponent isocyanate), (NH ₂, aldehydes), (NCO, polyamine), (NCO, multicomponent isocyanate), (NCO, polyvalent alcohol), (NCO, polynary epoxy), (OH, polyvalent alcohol), (OH, multi-halogenated compounds), (OH, polyamine), (OH, acid anhydrides).Wherein, from crosslinked, generate amino-formate bond, can form high-intensity crosslinked consideration, the combination of more preferably (functional group, linking agent)=(OH, polyvalent isocyanate).

As the object lesson of linking agent in the present invention, can there are below shown in the linking agent of structure.

[changing 9]

Such linking agent is to add in the coating fluid that contains above-mentioned polymerization initiated polymerization thing when the film forming of polymerization trigger layer.Then, the heat while filming by heat drying, carries out crosslinking reaction, can form firmly crosslinking structure.In more detail, by the addition reaction shown in the dehydration reaction shown in following ex1. (example 1) or ex2. (example 2), carry out crosslinking reaction, form crosslinking structure.As the temperature condition in these reactions, preferably 50 ℃ above below 300 ℃, more preferably 80 ℃ above below 200 ℃.

[changing 10]

And, as the addition of linking agent in coating fluid, according to the amount of the crosslinkable groups of introducing in polymerization initiated polymerization thing, change, from the residual impact on polyreaction of crosslinking degree or unreacted crosslinking component, consider, conventionally, the mole number with respect to crosslinkable groups, is preferably

equivalent, more preferably

equivalent, more preferably

equivalent.

And the solvent using when coating polymerization trigger layer, so long as can dissolve the solvent of above-mentioned polymerization initiated polymerization thing, is not particularly limited.From dry easiness, operability, consider, the preferred not too high solvent of boiling point, the concrete boiling point of can selecting is the solvent of left and right.

Concrete, can there are acetone, methylethylketone, hexanaphthene, vinyl acetic monomer, tetrahydrofuran (THF), toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, Acetyl Acetone, pimelinketone, methyl alcohol, ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy propyl yl acetate etc.

quality % is suitable.

The glue spread of the polymerization trigger layer that use polymerization initiated polymerization thing makes is from initiation energy or the film-forming properties consideration of surface grafting polymerization, and dried quality optimization is

more preferably

.

And then, in the present invention, as previously mentioned, while using the substrate of the layer on base material with insulative resin formation, in the layer forming at this insulative resin, preferably contain known polymerization starter, make the polymerization trigger layer of insulativity.The polymerization starter containing in polymerization trigger layer as this insulativity, be not particularly limited, for example can use on the side chain of recording in No. 10-45927, aforesaid thermal polymerization, Photoepolymerizationinitiater initiater (radical polymerization initiator, anionic polymerization initiator, cationic polymerization initiators) or No. 9-77891, Unexamined Patent, Unexamined Patent and there is the macromolecular compound of active carbonyl group, and on side chain, have polymerization cause can functional group and the polymkeric substance (polymerization initiated polymerization thing) of crosslinkable groups etc.

The amount of the polymerization starter containing in the polymerization trigger layer of insulativity general preferred in insulation layer with solid component meter the degree of quality %, more preferably

the degree of quality %.

The generation of graftomer

(a1) the generation form of graftomer in step, as previously mentioned, can be used the method for linked reaction, or photo-grafting polymerization.The method of this linked reaction is to utilize the method for the linked reaction of the reactive functional groups that the functional group that exists at substrate surface and macromolecular compound have on its end or side chain.

In the present invention, preferably use the substrate that forms polymerization trigger layer on base material, on this polymerization trigger layer, there is functional group's (interaction group) of forming with plating catalyst or its precursor phase mutual effect and the form ((a1-2) step) of the formation of the polymer layer that forms with the direct chemically combined polymkeric substance of this polymerization trigger layer.More preferably after the polymkeric substance that makes to have polymerizable group and interaction group on polymerization trigger layer contacts, by giving energy, the direct chemically combined form of (on the whole surface of polymerization trigger layer) this polymkeric substance on the whole surface of aforesaid substrate.Be that limit makes to comprise and has polymerizable group and contact with the composition of the compound of interaction group on polymerization trigger layer surface, limit is by the method for the direct combination of spike at this polymerization trigger layer Surface Creation.

Above-mentioned contact can be the substrate that dipping has formed polymerization trigger layer in the fluid composition that comprises the compound with polymerizable group and interaction group (polymer layer formation composition of the present invention), but consider from the viewpoint of operability or manufacture efficiency, as described later, preferably at the upper layer that forms composition (the polymer layer formation composition of the present invention) formation that comprises the compound with polymerizable group and interaction group by coating method of substrate surface (polymerization trigger layer surface).

In addition, in the manufacture method of the 3rd kind of surface metal mould material of the present invention, while forming polymer layer on the two sides of resin film as (a1 ") step, from easily form polymer layer on two sides simultaneously, consider, preferably use coating method.

The following describes in the present invention by surface grafting polymerization method the compound with polymerizable group and interaction group using while generating graftomer.

As the compound in the present invention with polymerizable group and interaction group, the polymer layer that the graftomer preferably generating forms meets above-mentioned

whole 4 conditions, the water-absorbent with polymerizable group and interaction group is all low, and then preferably uses the compound that hydrophobicity is high.

Preferably non-the dissociating property of interaction group in this compound functional group, non-dissociating property functional group refers to that functional group can not generate by dissociating the functional group of proton.

Even if such functional group has and plating catalyst or the interactional function of its precursor, because have high-hydroscopicity, wetting ability unlike the polar group (hydrophilic radical) of dissociating property, the polymer layer with the graftomer formation of this functional group can meet above-mentioned

condition.

In the present invention, polymerizable group is by giving energy; the compound that can make to have polymerizable group and interaction group mutually between or there is the compound of polymerizable group and interaction group and the functional group of substrate combination, concrete can there are active group in vinyl, vinyloxy group, allyl group, acryl, methacryloyl, oxetanyl, epoxy group(ing), isocyanate group, the functional group of containing active hydrogen, azo-compound etc.

As the interaction group in the present invention, preferably can form with metal ion the group of coordination, nitrogen-containing functional group, sulfur-bearing functional group, oxygen-containing functional group etc., concrete can there are imide group, pyridyl, tertiary amine groups, ammonium, pyrrolidone-base, amidino groups, the group that contains triazine ring structure, the group that contains cyamelide structure, nitro, nitroso-group, azo-group, diazo, azido-, cyano group, nitrogen-containing functional groups such as cyanate ester based (R-O-C N), ether, carbonyl, ester group, the group that contains N-oxide structure, the group that contains S-oxide structure, the oxygen-containing functional groups such as group that contain N-hydroxyl structure, thioether group, thioxy base, sulfoxide group, sulfuryl, sulfurous acid ester group, the group that contains sulfoxylic acid imines (sulfoxyimine) structure, the group that contains sulfonium salt (sulfoxynium) structure, the sulfur-bearing functional groups such as group of containing sulphonate structure, the phosphorous functional group such as phosphino-, contain chlorine, the group of the halogen atoms such as bromine, with unsaturated ethylene thiazolinyl etc.And, so long as show the form of non-dissociating property by the relation of adjacent atom or atomic group, also can use imidazolyl, urea groups, thioureido.

Wherein, high from polarity, to the sorptive power of plating catalyst etc. is high, consider, preferred ether (more particularly-O-(CH ₂) _n(n is-O- integer) structure that represents) or cyano group, most preferably cyano group.

General, polarity more high water absorbing capacity has higher tendency, because cyano group has in polymer layer, mutually gives up the such interaction of polarity, and it is fine and close that film becomes, and the decline of the polarity of polymer layer integral body, thereby water-absorbent reduces.And, in (a2) described later step, adsorptive catalyst in the good solvent of polymer layer, cyano group and solvent, the interaction between cyano group disappears, and become energy and plating catalyst interact.For the above reasons, the polymer layer with cyano group is not only low moisture absorption, and can well interact with plating catalyst, brings into play contrary performance and considers it is preferred.

And, as the interaction group in the present invention, more preferably alkyl cyano group.This is because aromatic series cyano group is to attract electronics on aromatic nucleus, and as the providing property of important unpaired electron such as the adsorptivity of plating catalyst etc. is reduced, alkyl cyano group is not joined on this aromatic nucleus, from the adsorptivity to plating catalyst etc., considers it is preferred.

In the present invention, the compound with polymerizable group and interaction group can be any form of monomer, macromole, polymkeric substance, wherein from the formative of polymer layer and the easiness of control, consider, preferably use polymkeric substance (polymkeric substance with polymerizable group and interaction group).

As the polymkeric substance with polymerizable group and interaction group, use has in the homopolymer or multipolymer that the monomer of interaction group obtains, introduced the polymkeric substance as Addition on ethylene polymerizability unsaturated groups (polymerizable group) such as the preferred vinyl of polymerizable group, allyl group, (methyl) propenyl, this polymkeric substance with polymerizable group and interaction group is at least on main chain end or side chain, to have the polymkeric substance of polymerizable group, preferably on side chain, has the polymkeric substance of polymerizable group.

As the monomer with interaction group using when obtaining the above-mentioned polymkeric substance with polymerizable group and interaction group, so long as there is the monomer of non-the dissociating property functional group of above-mentioned record, can use any monomer, for example concrete is what enumerate below.

They can use separately a kind, or two or more is combined with.

[changing 11]

[changing 12]

In thering is the polymkeric substance of polymerizable group and interaction group, from the viewpoint of the interaction formative with plating catalyst or its precursor, consider, derive from the unit of the monomer with interaction group, in thering is the polymkeric substance of polymerizable group and interaction group, preferably contain

% by mole scope, more preferably contain % by mole scope.

And, obtain while thering is the polymkeric substance of polymerizable group and interaction group, in order to reduce water-absorbent, and in order to improve hydrophobicity, also can use other monomers beyond the monomer with above-mentioned interaction group.As other monomers, general can use polymerizable monomer, can there are diene monomer, propylene base system monomer etc.Wherein, the propylene base system monomer of preferred unsubstituted alkyl.Concrete, can preferably use vinylformic acid tertbutyl ester, 2-ethylhexyl acrylate, butyl acrylate cores, vinylformic acid cyclohexyl ester, methacrylic acid benzyl ester etc.

The polymkeric substance like this with polymerizable group and interaction group can synthesize as following manner.

As synthetic method, can there are i) will there is the monomer and the method with the monomer copolymerizable of polymerizable group of interaction group, ii) monomer and the monomer copolymerizable with two key precursors of interaction group will be there is, then by the processing of alkali etc., introduce the method for two keys, iii) will there is the polymkeric substance and the monomer reaction with polymerizable group of interaction group, introduce the method for two keys (introducing polymerizable group).From synthetic adaptability, consider, preferred ii) will there is the monomer and the monomer copolymerizable with two key precursors of interaction group, then by processing such as alkali, introduce the method for two keys, iii) will there is the polymkeric substance and the monomer reaction with polymerizable group of interaction group, introduce the method for polymerizable group.

As the monomer with interaction group of use in thering is polymkeric substance synthetic of polymerizable group and interaction group, can use the monomer the same with the above-mentioned monomer with interaction group.Monomer can be used separately a kind of, also can two or more be combined with.

As the monomer with polymerizable group with thering is the monomer copolymerizable of interaction group, can there are (methyl) allyl acrylate, methacrylic acid 2-allyloxy ethyl ester etc.

And, as the monomer with two key precursors, can there are methacrylic acid 2-(the chloro-1-oxopropoxy of 3-) ethyl ester, methacrylic acid 2-(the bromo-1-oxopropoxy of 3-) ethyl ester etc.

And then, as the reaction that utilizes and have the functional group of carboxyl, amino or their salt, hydroxyl and epoxy group(ing) etc. in the polymkeric substance of interaction group, the monomer with polymerizable group using to introduce unsaturated group, has (methyl) vinylformic acid, (methyl) vinylformic acid glycidyl esters, allyl glycidyl ether, (methyl) vinylformic acid 2-isocyanatoethyl ester etc.

Below, illustrate and be applicable to the object lesson of the polymkeric substance with polymerizable group and interaction group of use in the present invention, but the invention is not restricted to these.

[changing 13]

[changing 14]

[changing 15]

Polymkeric substance as using in the manufacture method at a form surface metal mould material of the present invention, have polymerizable group and interaction group, preferably has interaction group---the polymkeric substance (being called " polymerizable polymer that contains cyano group " below) of cyano group.

The compound that the polymerizable polymer that contains cyano group of the present invention etc. has polymerizable group and interaction group, except polymerizable group and interaction group, also can have polar group.

Particularly, during surface metal mould material constructed in accordance, the polymer layer of formation is so long as meet above-mentioned

full terms, this polymkeric substance is by having polar group, by step described later, forms after metallic membrane, for example, while protective layer being set, can improve the bounding force of the contact area of polymer layer and protective layer.

As previously mentioned, in order to form polymer layer of the present invention, preferably use the fluid composition of the compound of the polymerizable group that contains the polymkeric substance etc. with polymerizable group and interaction group and interaction group, there is the compound of polymerizable group and interaction group and can dissolve the solvent of this compound composition (be preferably polymer layer formation composition of the present invention, its contain have cyano group or-O-(CH ₂) _n(n is-O- integer) structure representing and the polymkeric substance of polymerizable group and can dissolve the solvent of this polymkeric substance).

In addition, the content of the compound (polymerizable polymer that for example contains cyano group) with polymerizable group and interaction group in composition, all with respect to composition, be preferably 2 quality %

quality %.

The principal constituent that the solvent using in above-mentioned composition is composition, so long as can dissolve the compound with polymerizable group and interaction group, is not particularly limited.Also can in solvent, further add tensio-active agent.

As operable solvent, the carbonic ether series solvent of the ester series solvent of the nitrile series solvent of the acid amides series solvent of the ketone series solvent of the acid of the alkanol series solvent such as there are methyl alcohol, ethanol, propyl alcohol, ethylene glycol, glycerine, propylene glycol monomethyl ether, acetic acid and so on, acetone, methylethylketone, pimelinketone and so on, methane amide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone and so on, acetonitrile, propionitrile and so on, ritalin, vinyl acetic monomer and so on, dimethyl carbonate, diethyl carbonate and so on etc.

In them, when the polymerizable polymer that use contains cyano group is manufactured composition, preferred amide system, ketone system, nitrile series solvent, carbonic ether series solvent, concrete preferred acetone, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, acetonitrile, propionitrile, N-Methyl pyrrolidone, dimethyl carbonate.

And during the composition that comprises the polymerizable polymer that contains cyano group in coating, from easy to operate consideration, preferably boiling point is

solvent.In addition, these solvents can be used alone, but also also mix together.

And, in the present invention, while being coated with the composition that contains the compound with polymerizable group and interaction group on substrate or polymerization trigger layer, can select the suction solvent rate of substrate or polymerization trigger layer to be

solvent.The base material that floods substrate or formation polymerization trigger layer in solvent, while taking out after 1000 minutes, this suction solvent rate can be tried to achieve from the variation of quality.

And, while being coated with the composition that contains the compound with polymerizable group and interaction group on substrate or polymerization trigger layer, also can select the swelling rate of substrate or polymerization trigger layer to be solvent.The base material that floods substrate or formation polymerization trigger layer in solvent, while taking out after 1000 minutes, this swelling rate can be tried to achieve from variation in thickness.

The tensio-active agent that can add in solvent as required, tensio-active agent is so long as be dissolved in goods in solvent just, as such tensio-active agent example, if there are, the anionic surfactant of positive sodium lauryl benzene sulfonate and so on, or the cationic surfactant of positive lauryl trimethyl ammonium chloride and so on, polyoxyethylene nonyl phenolic ether is (as commercially available product, for example there is エマ Le ゲ Application (Ye Malu lid) 910, KAO. Corp. SA's manufacture etc.), polyoxyethylene sorbitan monolaurate (commercially available product is such as there being trade(brand)name " Star イ mono-Application 20 " (thatch mattress 20) etc.), the nonionic surfactant of polyoxyethylene lauryl ether and so on etc.

And, can add softening agent as required.As operable softening agent, can use general softening agent, phthalate (dimethyl esters, diethyl ester, dibutyl ester, two-2-(ethyl hexyl) ester, di-n-octyl ester, diisononyl esters, dinonyl ester, diiso decyl ester, butyl benzyl ester), adipic acid ester class (dioctyl ester, diisononyl esters), dioctyl azelate, sebacic acid ester (dibutyl ester, dioctyl ester) tricresyl phosphate benzyl ester, ethanoyl citric acid tributyl ester, epoxidised soybean oil, trioctyl trimellate, clorafin or N,N-DIMETHYLACETAMIDE, the such high boiling solvent of N-Methyl pyrrolidone also can be used.

In the composition that contains the compound with polymerizable group and interaction group, can add polymerization retarder as required.The polymerization retarder that can use has Resorcinol, ditert-butylhydro quinone, 2,5-two (1,1,3,3-tetramethyl butyl) phenol, benzoquinones class, the TEMPO (2 such as hydroquinone type, p methoxy phenol, phenol such as Resorcinol, 2,6,6-tetramethyl--1-piperidines oxyradical), nitroso-group amine, the catechols such as radical type, phenothiazines, N-nitroso-group phenyl oxyamine, its aluminium salt such as 4-hydroxyl TEMPO.

And, in the composition that contains the compound with polymerizable group and interaction group, in order to promote solidifying of polymerization trigger layer, can add solidifying agent and/or curing catalyst as required.As solidifying agent and curing catalyst, can use known product.Concrete, as curing catalyst, the having aliphatic polyamines, alicyclic polyamine, aromatic series polyamine, polymeric amide, acid anhydrides, phenol, phenolic aldehyde, polythiol, there is the compound of 2 above active hydrogens etc. of addition polymerization type, as catalyst type, can there are aliphatic tertiary amine, aromatic nitrile base, imidazolium compounds, Lewis acid complex compound etc.

And, as passing through heat, light, moisture, pressure, acid, alkali etc. cause curing goods, can there are diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diethyl amino propylamine, daiamid, メ Application セ Application (continuous plug) diamines, isophorone diamine, N-aminoethyl piperazine, two (the 3-aminopropyls)-2,4,8 of 3,9-, 10-tetra-oxygen volution (5,5) undecane adductss, two (4-amino-3-methylcyclohexyl) methane, two (4-aminocyclohexyl) methane, toluylenediamine, diaminodiphenyl-methane, between penylene diamines, diamino diphenyl sulfone, dicyano diamide, hexanodioic acid ジヒラジ De (Ji Heilaji bucket), Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl norbornene dioic anhydride, lauryl succinyl oxide, chlorendic acid acid anhydride, PMA, benzophenone tetracarboxylic anhydride, ethylene glycol bis (trimellitate), tetrahydrotoluene tetracarboxylic anhydride, trihemellitic acid acid anhydride, poly-nonane diacid acid anhydride, phenol aldehyde, xylylene phenolic aldehyde, dihydroxyphenyl propane aldehyde, triphenyl methane phenolic aldehyde, xenyl phenolic aldehyde, Dicyclopentadiene (DCPD) phenolic aldehyde, terpenes phenol aldehyde, polythiol, polythioether, 2,4,6-tri-(dimethylaminomethyl) phenol, 2,4,6-tri-(dimethylaminomethyl) phenol-tri--2-ethylhexyl hydrochlorate, benzyl dimethyl amine, 2-(dimethylaminomethyl) phenol glyoxal ethyline, 2-ethyl-4-methylimidazole 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl S-triazine, BF ₃mono aminoethane complex compound, Lewis acid complex compound, organic acid hydrazides, diamino Malaysia acyl cyanide, melamine derivative, imdazole derivatives, polyamine salt, amine group with imine moiety, aromatic series diazonium salt, diallyl salt compounded of iodine, triallyl sulfonium salt, triallyl selenium salt, ketimine compound etc.

These solidifying agent and/or curing catalyst be from the considerations such as adaptation of coating and substrate or the electroplating film of solution, preferably adds with the nonvolatile component except residual after desolventizing

quality % degree.And solidifying agent and/or curing catalyst can add in polymerization trigger layer, now add the amount in polymerization trigger layer to and add the preferred above-mentioned scope of summation amount in polymer layer to.

And, and then can add rubber constituent (such as carboxyl terminal butadiene acrylonitrile (CTB N)), fire retardant (such as phosphorus flame retardant), thinner or thixotropic agent, pigment, defoamer, flow agent, coupling agent etc.And, also can in polymerization trigger layer, add these additives as required.

These compound and suitable mixing of various additive with polymerizable group and interaction group are used as composition, and the physical property of the polymer layer of formation such as thermal expansivity, second-order transition temperature, Young's modulus, Poisson's ratio, rupture stress, yielding stress, heat decomposition temperature etc. can carry out most suitable setting.Particularly preferably rupture stress, yielding stress, a side that heat decomposition temperature is higher.

The polymer layer obtaining can be measured heat durability in temperature cycling test or heat ageing test, backflow test etc.For example, about thermolysis, can under 200 ℃ of environment, expose 1 hour, weight is reduced to being evaluated as below 20% and has sufficient heat durability.

When containing the composition with polymerizable group and the compound of interaction group and contact, its glue spread, from considering with the sufficient interaction formative of plating catalyst or its precursor, is converted into solids component and is preferably 0.1～10g/m ², be particularly preferably 0.5～5g/m ².

In addition, the composition that coating contains the compound with polymerizable group and interaction group on substrate, dry, when layer that formation contains the compound with polymerizable group and interaction group, between being coated with and being dried, can transfer and set to 0 .5～2 hour at 20～40 ℃, remove remaining solvent.

Providing of energy

The method that has for example use heating or exposure israds to irradiate that provides the method for energy to enumerate to substrate surface.The useful UV lamp of example of the method, visible ray etc. carry out rayed, use the heating such as hot plate etc.As the light source using in the method, such as having mercuryvapour lamp, metal halid lamp, xenon lamp, chemical lamp, carbon arc lamp etc.The example of radioactive rays has electron rays, x-ray, ionic fluid, far infrared rays etc.And also can use g line, i line, UV light far away, high density energy bundle (laser beam).

As the concrete form of general use, suitable have the heat of use record first-class direct imaging record, with infrared laser scan exposure, with the high brightness flash exposures such as xenon discharge lamp or infrared(ray)lamp exposure etc.

Provide the growing amount of the graftomer that time of energy requirement can target and light source and difference, be generally 10 seconds～between 5 hours.

In addition, while providing energy to expose, its exposure power is in order easily to carry out graft polymerization, and can suppress the decomposition of the graftomer that generates, preferably 10mJ/cm ²～5000mJ/cm ²scope, more preferably 50mJ/cm ²～3000mJ/cm ²scope.

And, as the compound with polymerizable group and interaction group, use that molecular-weight average is more than 20,000, the polymerization degree is polymkeric substance more than 200 structural units, because easily carry out graft polymerization under low-energy exposure, more can suppress the decomposition of the graftomer of generation.

According to (a1) described above step, can on substrate, form the polymer layer (graft polymer layer) being formed by the graftomer with interaction group.

The polymer layer obtaining for example adds in the basic solution of pH12, and while stirring 1 hour, the decomposition at polymerizable group position following in the situation that, can be carried out to this polymer layer the cleaning of high alkalinity solution 50%.

(a1 ') step

In the manufacture method of the 2nd kind of surface metal mould material of the present invention, in (a1 ') step, on substrate, form the polymer layer that there is cyano group and form with the direct chemically combined polymkeric substance of this substrate.

In this step as thering is the compound of polymerizable group and interaction group in above-mentioned (a1) step, except use has the compound of polymerizable group and cyano group, using the same method of method of recording with (a1) step, is preferred equally.

By this (a1 ') step, can on substrate, form and there is the polymer layer (graft polymer layer) that the graftomer of cyano group forms.

Form the polymkeric substance of the polymer layer obtaining in this step as having cyano group with the functional group of plating catalyst or its precursor phase mutual effect formation.This cyano group as previously mentioned, polarity is high, high to the sorptive power of plating catalyst etc., but because do not have such high-hydroscopicity, the wetting ability of dissociating property polar group (wetting ability base), the polymer layer water-absorbent consisting of the graftomer with this cyano group is low, and hydrophobicity is high.

(a2) step

(a2), in step, in the polymer layer forming, provide plating catalyst or its precursor in above-mentioned (a1) or (a1 ') step.In this step, the interaction base (cyano group) that the graftomer of formation polymer layer has, according to its function, adsorbs the plating catalyst or its precursor that provide.

Here, as plating catalyst or its precursor, in aftermentioned (a3) plating step, that can enumerate has a material as the function of plating catalyst or electrode.Therefore, plating catalyst or its precursor decide according to electroplating kind in (a3) plating step.

In addition, here, the plating catalyst using in this step or its precursor be electroless plating catalyzer or its precursor preferably.

Electroless plating catalyzer

The electroless plating catalyzer using in the present invention so long as active nucleus during electroless plating can use arbitrarily.Its example has the metal (than Ni ionization tendency known metal low, energy electroless plating) of the catalysis energy with self catalyzed reduction reaction.Object lesson has Pd, Ag, Cu, Ni, Al, F e, Co etc.Wherein, the metal of preferred energy polygamy position.Species number, the catalysis of the functional group of special consideration energy coordination can be high, preferably Pd.

This electroless plating catalyzer can be used as metallic colloid.Common metal colloid is in the solution that charged tensio-active agent or charged protective material exist, and by reducing metal ion, manufactures.The electric charge of metallic colloid can regulate by tensio-active agent or the protective material of use.

Electroless plating catalyst precursor

The electroless plating catalyst precursor using in this step so long as can make electroless plating catalyzer by chemical reaction, is not particularly limited.The metal ion of the metal that the above-mentioned electroless plating catalyzer of main use is enumerated.Electroless plating catalyst precursor is that metal ion becomes electroless plating catalyzer 0 valency metal by reduction reaction.Electroless plating catalyst precursor is after metal ion is provided in polymer layer, before the dipping of bathing at electroless plating, can become by other reduction reaction 0 valency metal, as electroless plating catalyzer, also electroless plating catalyst precursor former state can be immersed in to electroless plating and bathe, the reductive agent in bathing by electroless plating becomes metal (electroless plating catalyzer).

In fact, electroless plating precursor metal ion is to use metal-salt to be provided on polymer layer.In the metal-salt using, so long as be dissolved in the material that is dissociated into metal ion and alkali (negatively charged ion) in applicable solvent, be not particularly limited.Object lesson has M (NO ₃) _n, MCln, M _2/n(SO ₄), M _3/n(PO ₄) (M is the atoms metal of n valency) etc.As metal ion, the ion that can compatibly use above-mentioned metal-salt to dissociate.Object lesson for example has Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, Pd ion.Ion that wherein preferably can polygamy position.Consider species number and the catalysis energy of the functional group of energy coordination, particularly preferably Pd ion.

As the metal of electroless plating catalyzer or electroless plating precursor metal salts are provided to the method in polymer layer, can be in suitable dispersion medium dispersed metal dispersion liquid or in suitable solvent dissolved metal salt, the solution that preparation comprises the metal ion dissociating, on polymer layer, be coated with this dispersion liquid or solution, or flood the substrate that forms polymer layer in this dispersion liquid or solution.

And, in (a1) or (a1 ') step, while using surface grafting polymerization method, the composition that contact contains the compound with polymerizable group and interaction group (cyano group) on substrate, the method that also can add electroless plating catalyzer or its precursor in composition.Containing the compound with polymerizable group and interaction group (cyano group) contacts on substrate with the composition of electroless plating catalyzer or its precursor, by applicable surface grafting polymerization method, can form and there is interaction group (cyano group) and contain the polymer layer with the direct chemically combined polymkeric substance of substrate, plating catalyst or its precursor.In addition, by using the method, (a1) of the present invention or (a1 ') step and (a2) step can be carried out with a step.

In addition, process in the manufacture method of the 3rd kind of surface metal mould material of the present invention (a1 ") step; when the two sides of resin film is formed to polymer layer, in order to make the polymer layer on this two sides contact electroless plating catalyzer or its precursor simultaneously, preferably use above-mentioned pickling process.

Contact as described so under electroless plating catalyzer or its precursor, in polymer layer, the upper interaction by the such intermolecular forces of Van der Waals force of interaction property group (cyano group) or utilization, by the interaction of the coordinate bond of lone electron pair, can be adsorbed electroless plating catalyzer or its precursor.

Consider fully to adsorb, in dispersion liquid, solution, composition, metal concentration or GOLD FROM PLATING SOLUTION belong to the scope that ionic concn is preferably 0.001～50 quality %, more preferably the scope of 0.005～30 quality %.And, be preferably 30 seconds duration of contact～about 24 hours, about more preferably 1 minute～1 hour.

Other catalyzer

In the present invention, in (a3) described later step, polymer layer is not carried out electroless plating and carries out the catalyzer that Direct Electrolysis electroplate to use and can use 0 valency metal.The example of this 0 valency metal has Pd, Ag, Cu, Ni, Al, Fe, Co etc.Metal that wherein preferably can polygamy position.Consideration can be high to the absorption of interaction group (cyano group) (paying) property, catalysis, preferably Pd, Ag, Cu.

Through (a2) described above step, between interaction group (cyano group) that can be in polymer layer and plating catalyst or its precursor, form and interact.

(a3) step

(a3), in step, to providing the polymer layer of electroless plating catalyzer or its precursor to electroplate, form electroplating film.The electroplating film forming has good electroconductibility, adaptation.

The plating kind of carrying out in this step has electroless plating, metallide etc., in above-mentioned (a2) step, forms the function of interactional plating catalyst or its precursor between can selective polymer layer.

In other words, in this step, for providing the polymer layer of plating catalyst or its precursor can carry out metallide, also can carry out electroless plating.

Wherein, in the present invention, consider to improve formative and the adaptation of the mixed structure occurring in polymer layer, preferably carry out electroless plating.And in order to obtain the electrolytic coating of expectation thickness, more preferably after electroless plating, carry out metallide.

The following describes and in this step, be applicable to the plating carried out.

Electroless plating

Electroless plating refers to as electroplating and uses the solution that can dissolve the metal ion of separating out, by the operation of chemical reaction precipitating metal.

Electroless plating in this step is for example to providing the substrate of electroless plating catalyzer to wash, and removes after residual electroless plating catalyzer (metal), is immersed in electroless plating bath and carries out.As the electroless plating using, bathe and can use general known electroless plating to bathe.

And, providing the substrate of electroless plating catalyst precursor to be immersed in electroless plating made it in bathing in polymer layer absorption or dipping electroless plating catalyst precursor state lower time, water cleaning base plate, removes after residual precursor (metal-salt etc.), dipping in bathing to electroless plating.Now, electroless plating carries out the reduction of plating catalyst precursor and carries out continuously electroless plating in bathing.Electroless plating used herein is bathed and can be used and above-mentioned the same, general known electroless plating bath.

In addition, the reduction of electroless plating catalyst precursor is except being used above-mentioned electroless plating liquid, and (reduced liquid carries out other steps before electroless plating also can to prepare catalyst activity liquid.Catalyst activity liquid is to have dissolved electroless plating catalyst precursor (being mainly metal ion) to be reduced into the liquid of the reductive agent of 0 valency metal, with respect to the concentration of this precursor of total amount of liquid, be generally the scope of 0.1 quality %～50 quality %, preferably 1%～30% scope.It is the reductive agents such as reductive agent, formaldehyde, Hypophosporous Acid, 50 that the example of the reductive agent that can use has sodium borohydride, the such boron of ヂメチ Le アミ Application methylamine borine.

The composition of bathing as general electroless plating, except solvent, mainly contains the metal ion of 1. plating use, 2. reductive agent, the 3. additive (stablizer) of the stability of raising metal ion.In this plating bath, except above-mentioned substance, also can contain the known additives such as stablizer of plating bath.

In the solvent using in this plating bath, preferably, polymer layer (simultaneously meet the polymer layer of above-mentioned condition 1～4) that hydrophobicity high low with respect to water-absorbent, contains the organic solvent that affinity is high.The kind of organic solvent is selected and content can suitably be selected according to the physical property of polymer layer.When in the condition 1 of polymer layer, saturated water absorption is larger especially, preferably the containing ratio of organic solvent is few.Concrete is as follows:

; when in condition 1, saturated water absorption is 0.01～0.5 quality %; in whole solvents of plating bath, the content of organic solvent is preferably 20～80 quality %; when saturated water absorption is 0.5～5 quality %; in whole solvents of plating bath, the content of organic solvent is preferably 10～80 quality %; when saturated water absorption is 5～10 quality %; in whole solvents of plating bath, the content of organic solvent is preferably 0～60 quality %; when saturated water absorption is 10～20 quality %, in whole solvents of plating bath, the content of organic solvent is preferably 0～45 quality %.

As the organic solvent using in plating bath, must be the solvent that can be used in water, from this point, consider, preferably use the alkanols such as the ketones such as acetone, methyl alcohol, ethanol, Virahol.

The kind of the metal using in bathing as electroless plating, known have copper, tin, lead, nickel, gold, palladium, a rhodium, wherein considers electroconductibility, particularly preferably copper, gold.

And, have optimal reductive agent, additive corresponding to above-mentioned metal.For example, during the electroless plating of copper is bathed, contain the CuSO as mantoquita ₄, as the HCOH of reductive agent, as sequestrant, three alkanolamines etc. such as the stablizer EDTA of Additive Cu ion or Rochelle salts.And, in the plating bath using, contain rose vitriol, single nickel salt, the sodium hypophosphite as reductive agent, the sodium malonate as sequestrant, sodium malate, sodium succinate as its metal-salt in the electroless plating of CoNiP.And, in the electroless plating of palladium is bathed, contain (Pd (the NH as metal ion ₃) ₄) Cl ₂, as the NH of reductive agent ₃, H ₂nNH ₂, as the EDTA of stabilization agent.In these plating baths, also can add the composition except mentioned component.

The thickness of the electroplating film being formed by such electroless plating can be controlled by the concentration of metal ions of plating bath, dipping time in plating bath or temperature of plating bath etc.From electroconductibility, consider, more than this thickness is preferably 0.5 μ m, more preferably more than 3 μ m.

And, at the dipping time of plating bath, be preferably 1 minute～about 6 hours, about more preferably 1 minute～3 hours.

The electroplating film of the electroless plating by above acquisition is observed section by scanning electron microscope (scanning electron microscope:SEM), can confirm that the micropartical that consists of electroless plating catalyzer or plated metal in polymer layer disperses with high-density, and and then on polymer layer, separate out plated metal.On the interface of substrate and electroplating film because polymkeric substance and atomic admixture, for example, even if the interface of substrate (organic composition) and inorganics (catalyst metal or plated metal) is level and smooth (concavo-convex difference is that 500nm is following), adaptation is good.

Metallide

In this step, when the plating catalyst (a2) providing in step or its precursor have as the function of electrode, can be to providing the polymer layer of this catalyzer or its precursor to carry out metallide.

And, also can, after aforesaid electroless plating, using the electroplating film forming as electrode, and then carry out metallide.Using the good electroless plating film of the adaptation with substrate as matrix, then can easily form the metallic membrane with new any thickness thus.Like this, after electroless plating, carry out metallide, because metallic membrane can form the thickness of target, metallic membrane of the present invention can be suitable in various application.

As electro-plating method of the present invention, can use current known method.In addition, the metal example using in the metallide as this step, has copper, chromium, lead, nickel, gold and silver, tin, zinc etc.From electroconductibility, consider preferably copper, gold and silver, more preferably copper.

The thickness of the metallic membrane obtaining by metallide is different according to purposes, can regulate the metal concentration that contains in plating bath or current density etc. to control.In addition, the thickness using in general electric distribution etc. is considered from electroconductibility, preferably more than 0.5 μ m, more preferably more than 3 μ m.

In the present invention, from the metal of aforesaid plating catalyst, plating catalyst precursor or metal-salt and/or the metal of separating out by electroless plating, by form the microstructure of minute shape in this layer, can further improve the adaptation of metallic membrane and polymer layer in polymer layer.

The amount of metal existing in polymer layer can be taken pictures to substrate section with metalloscope, the ratio of discovery from the most surface of polymer layer to the shared metal in region of the degree of depth 0.5 μ m is 5～50 area %, when the arithmetic average roughness Ra of polymer layer and metal interface (ISO4288 (1996)) is 0.05 μ m～0.5 μ m, show stronger bounding force.

Surface metal mould material

The manufacture method of surface metal mould material of the present invention, through each step, can obtain surface metal mould material of the present invention.In addition, as long as be applicable to the manufacture method of the 3rd kind of surface metal mould material of the present invention, can obtain the surface metal mould material that has formed metallic membrane on two sides.

Even if the surface metal mould material that the manufacture method by surface metal mould material of the present invention obtains under hot and humid, has the equable effect of bounding force with metallic membrane.This surface metal mould material is such as can be for such as anti electromagnetic wave film, coated film, 2 layers of CCL (Copper Clad Laminate) material, electric various uses such as material for distribution.

The manufacture method of metal pattern material of the present invention is through step (a1)～(a3), the electroplating film with the surface metal mould material of the present invention of acquisition is the etched step of pattern-like.

The following describes this etching step (a4).

(a4) step

(a4), in step, the electroplating film (metallic membrane) forming in above-mentioned (a3) step is to pattern-like etching.Be in this step, by etching, remove the unwanted part of electroplating film forming on the whole surface of substrate, can form the metal pattern of expectation.

In the formation of this metal pattern, can use any method, concrete can use general known elimination method, half add.

Elimination method refers on the electroplating film forming dry film resist layer is set, and by pattern exposure, the formation pattern identical with metal pattern portion that develop, uses dry film corrosion-resisting pattern as mask, with etching solution, removes electroplating film, forms the method for metal pattern.As dry film resist layer, can use any material, for example the goods of minus, eurymeric, aqueous, film like.And, as engraving method, can use any method of using when the manufacture of printed wiring board, can use Wet-type etching, dry etching etc., can select arbitrarily.From easy considerations such as operation and devices, preferred Wet-type etching.As the example of the etching solution that can use, that can enumerate has aqueous solution such as cupric chloride, iron(ic) chloride.

And, half add refers on the electroplating film forming dry film resist layer is set, by pattern exposure, development, form the pattern identical with nonmetal mold portion, using dry film corrosion-resisting pattern as mask, electroplate, remove after dry film corrosion-resisting pattern, implement fast etching, by electroplating film is to pattern-like, remove, form the method for metal pattern.As materials such as dry film レジソト, etching solutions, can use and material the same in elimination method.And, as electro-plating method, can use the method for above-mentioned record.

Through above-mentioned steps (a1)～(a4), manufacture has the metal pattern material of the metal pattern of expectation.

On the other hand, the polymer layer obtaining in step (a1) or (a1 ') is formed to pattern, the polymer layer of pattern-like is carried out to step (a2) and (a3), can manufacture metal pattern material (full additive method).

As the polymer layer obtaining in step (a1) or (a1 '), form the method for pattern-like, concrete is to provide energy to form pattern when forming polymer layer, and will not provide the part of energy to develop to remove, form the polymer layer of pattern-like.

In addition, as developing method, in order to form the polymer layer of the compound etc. with polymerizable group and interaction group (cyano group), to be immersed in the solvent that can dissolve the material using.Dipping time is preferably 1 minute～scope of 30 minutes.

And, (a1) or the polymer layer of (a1 ') can use the known coating processes such as spraying method of woodburytype, ink jet method, use mask, directly form after pattern, energy is provided, then, develop and form.

For to form the step (a2) of electroplating film on the polymer layer of pattern identical with aforesaid method with (a3) step forming.

Metal pattern material

Metal pattern material of the present invention obtains by the manufacture method of above-mentioned metal pattern material of the present invention.

Form the polymer layer of the metal pattern material obtaining as previously mentioned, water-absorbent is low, hydrophobicity is high, thereby the insulation reliability of the exposed division of this polymer layer (the non-formation region of metal pattern) is good.

In the concavo-convex difference on surface, to be preferably that the substrate of (more preferably below 100nm) below 500nm is whole arrange metallic membrane (electroplating film) to metal pattern material of the present invention comprehensively or on part.And, more than the adaptation of substrate and metal pattern is preferably 0.2kN/m.That is,, even if substrate surface is level and smooth, the adaptation of substrate and metal pattern is also good.

In addition, the concavo-convex difference of substrate surface can be by vertically cutting off substrate with respect to substrate surface, the value that this section is observed to measure with SEM.

In more detail, the Rz of the substrate surface of measuring based on ISO4287 (1997), " in given side, from being up to mean value and poor from the mean value of 5 the lowest point of minimum to the of the Z data on the 5th mountain top " is preferably below 500nm.

And, the value of the adaptation of substrate and metallic membrane is with epoxy, to be the bonding copper coin (thickness: 0.1mm) of tackiness agent (trade(brand)name: アラ Le ダイト (I Shandong paddy one throw), チバガイギ mono-(very cling to Ga mono-to) manufacture) on the surface of metallic membrane (metal pattern), dry after 4 hours at 140 ℃, based on JISC6481 (the known printing distributing board of IEC60249-1 (1982) is opened laminated plate test method with copper), carry out 90 degree peel tests, or directly strip the end of metallic membrane itself, based on JISC6481, carry out the value that 90 degree peel tests obtain.

The metal pattern material that manufacture method by metal pattern material of the present invention obtains is such as being applicable in the various uses such as semi-conductor chip, various electric wiring board, FPC (flexible print circuit), COF (Chip On Film), TAB (automatic bonding band), antenna, multi-layered wiring board, motherboard.

Novel polymer

The novel polymer providing as a form of the present invention is the multipolymer that contains the unit that unit that following formula (1) represents and following formula (2) represent.This novel polymer is an example according to the above-mentioned polymerizable polymer that contains cyano group using in the manufacture method of the surface metal mould material of a form of the present invention.Below this novel polymer is called aptly " polymerizable polymer that contains itrile group ", is elaborated.

[changing 16]

Formula (1) formula (2)

In above-mentioned formula (1) and formula (2), R ¹～R ⁵represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, X, Y and Z represent respectively singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether, L independently ¹and L ²represent independently respectively to replace or unsubstituted divalent organic group.

R ¹～R ⁵while being replacement or unsubstituted alkyl, as unsubstituted alkyl, that can enumerate has methyl, ethyl, propyl group, a butyl, and as substituted alkyl, the methyl, ethyl, propyl group, the butyl that have methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atom etc. to replace that can enumerate.

In addition, as R ¹, preferred hydrogen atom, methyl or the methyl replacing with hydroxyl or bromine atoms.

As R ², preferred hydrogen atom, methyl or the methyl replacing with hydroxyl or bromine atoms.

As R ³, preferred hydrogen atom.

As R ⁴, preferred hydrogen atom.

As R ⁵, preferred hydrogen atom, methyl or the methyl replacing with hydroxyl or bromine atoms.

When X, Y and Z are replacement or unsubstituted divalent organic group, as the organic group of this divalence, having of enumerating replaces or unsubstituted aliphatic alkyl, replacement or unsubstituted aromatic hydrocarbyl.

As replacing or unsubstituted aliphatic alkyl, preferred methylene base, ethylene group, trimethylene base, fourth support group or these groups that for group, methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atom etc. replace.

As replacing or unsubstituted aromatic hydrocarbyl, preferred unsubstituted phenyl or the phenyl replacing with methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atom etc.

Wherein, preferably-(CH ₂) _n-(integer that n is 1～3), more preferably-CH ₂-.

L ¹the divalent organic group preferably with amino-formate bond or urea key, more preferably has the divalent organic group of amino-formate bond, and wherein preferably total carbon atom number is 1～9.In addition, here, L ¹total carbon atom number refer to and use L ¹the total carbon atom number containing in the replacement representing or unsubstituted divalent organic group.

More specifically, L ¹the structure that represented by following formula (1-1) or formula (1-2) of structure optimization.

[changing 17]

Formula (1-1) formula (1-2)

In above-mentioned formula (1-1) and formula (1-2), R ^aand R ^brespectively to use 2 divalent organic groups that above atom forms that are selected from carbon atom, hydrogen atom and Sauerstoffatom independently, as preferred example, having of can enumerating replaces or unsubstituted, methylene base, ethylene group, trimethylene base or fourth support group, Oxyranyle, diepoxide for example base, three Oxyranyles, Fourth Ring oxirane group, diepoxy propyl, three propylene oxide bases, Fourth Ring Ethylene Oxide base.

And, L ²the group of the alkylene base of straight chain, branching or ring-type, aromatic series base or these moiety combinations preferably.By the group of this alkylene base and the combination of aromatic series base, and then can insert ether, ester group, amide group, carbamate groups, urea groups.Wherein, L ²preferably total carbon atom number is 1～15, particularly preferably unsubstituted.In addition, here, L ²total carbon atom number refer to L ²the total carbon atom number containing in the replacement representing or unsubstituted divalent organic group.

As object lesson, that can enumerate has methylene base, ethylene group, trimethylene base, fourth support group, penylene base and these groups that for group, methoxyl group, hydroxyl, chlorine atom, bromine atoms, fluorine atom etc. replace, and then can be their combination.

The unit that has above-mentioned formula (1) to represent that the preferred example of the polymerizable polymer that contains itrile group of the present invention can be enumerated is the polymkeric substance of the unit of following formula (3) expression.

[changing 18]

Formula (3)

In above-mentioned formula (3), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, Z represents singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether, W represents that (R is hydrogen atom or alkyl for Sauerstoffatom or N R, preferably represent the not substituted alkyl that hydrogen atom or carbonatoms are 1～5), L ¹represent to replace or unsubstituted divalent organic group.

R in formula (3) ¹and R ²with the R in above-mentioned formula (1) ¹and R ²equivalent in meaning, preferred example is also identical.

Z in Z in formula (3) and above-mentioned formula (1) is equivalent in meaning, and preferred example is also identical.

And the L in formula (3) ¹also with above-mentioned formula (1) in L ¹equivalent in meaning, preferred example is also identical.

The polymerizable polymer that contains itrile group as the present invention, the unit that preferred above-mentioned formula (3) represents is the polymkeric substance of the unit of following formula (4) expression.

[changing 19]

Formula (4)

In formula (4), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl, V and W represent that respectively (R represents hydrogen atom or alkyl, preferably the not substituted alkyl of hydrogen atom or carbonatoms 1～5 for Sauerstoffatom or N R independently.), L ¹represent to replace or unsubstituted divalent organic group.

R in formula (4) ¹and R ²with the R in above-mentioned formula (1) ¹and R ²equivalent in meaning, preferred example is also identical.

L in formula (4) ¹with the L in above-mentioned formula (1) ¹equivalent in meaning, preferred example is also identical.

W in above-mentioned formula (3) and formula (4) is preferably Sauerstoffatom.

And, in above-mentioned formula (3) and formula (4), L ¹be preferably unsubstituted alkylene base or there is amino-formate bond or the divalent organic group of urea key, more preferably there is the divalent organic group of amino-formate bond, the group that in them, particularly preferably total carbon atom number is 1～9.

And, the polymerizable polymer that contains itrile group as the present invention, the unit that preferred above-mentioned formula (2) represents is the unit that following formula (5) represents.

[changing 20]

Formula (5)

In above-mentioned formula (5), R ⁵represent hydrogen atom or replacement or unsubstituted alkyl, U represents Sauerstoffatom or N R ' (R ' represents hydrogen atom or alkyl, is preferably the not substituted alkyl of hydrogen atom or carbonatoms 1～5), L here ²represent to replace or unsubstituted divalent organic group.

R in formula (5) ⁵with the R in above-mentioned formula (1) ¹and R ²equivalent in meaning, preferred hydrogen atom.

And, the L in formula (5) ²with the L in above-mentioned formula (1) ²equivalent in meaning, be preferably the alkylene base, aromatic series base of straight chain, branching or ring-type or the group after their combinations.

Especially, in formula (5), L ²in there is straight chain with having of enumerating of the linking part potential energy of cyano group, the divalent organic group of the alkylene base of branching or ring-type, wherein, this divalent organic group more preferably total carbon atom number is 1～10.

And, as other preferred forms, the L in formula (5) ²in with the bond sites of cyano group be the divalent organic group with aromatic group, wherein the preferred total carbon atom number of this divalent organic group is 6～15.

The polymerizable polymer that contains itrile group of the present invention is the structure that comprises the unit that above-mentioned formula (1)～formula (5) represents, has the polymkeric substance of polymerizable group and itrile group on side chain.

This polymerizable polymer that contains itrile group for example can synthesize by mode below.

The kind of the polyreaction during as the synthetic polymerizable polymer that contains itrile group of the present invention, that can enumerate has radical polymerization, cationoid polymerisation, anionoid polymerization.From controlling the angle of reaction, consider, preferably use radical polymerization, cationoid polymerisation.

The polymerizable polymer that contains itrile group of the present invention is 1) form the polymeric species of main polymer chain when different with the polymeric species of introducing polymerizable group at side chain, 2), when the polymeric species that forms main polymer chain is identical with the polymeric species of introducing polymerizable group on side chain, its synthetic method is different.

1) when the polymeric species of formation main polymer chain is different from the polymeric species of introducing polymerizable group on side chain

Form the polymeric species of main polymer chain when different from the polymeric species of introducing polymerizable group on side chain, being divided into 1-1) main polymer chain forms and to be undertaken by cationoid polymerisation, the polymeric species of introducing polymerizable group on side chain is the form of radical polymerization, 1-2) main polymer chain formation is radical polymerization, and the polymeric species of introducing polymerizable group on side chain is the form of cationoid polymerisation.

1-1) main polymer chain formation is cationoid polymerisation, and the polymeric species of the polymerizable group of introducing on side chain is the form of radical polymerization

In the present invention, it is cationoid polymerisation that main polymer chain forms, the polymeric species of the polymerizable group of introducing on side chain be the monomer that uses in the form of radical polymerization can enumerate have a following compound.

Be used to form the monomer of the unit that contains polymerizable group

In this form, use be used to form the unit that contains polymerizable group and the monomer using has vinyl (methyl) acrylate, allyl group (methyl) acrylate, 4-(methyl) acryl butane-ethylene base ether, 2-(methyl) acryl ethane and ethylene base ether, 3-(methyl) acryl propane vinyl ether, (methyl) acryloxy Diethylene Glycol vinyl ether, (methyl) acryloxy triethylene glycol vinyl ether, (methyl) acryl 1st terpinol, 1-(methyl) acryloxy-2-methyl-2-propylene, 1-(methyl) acryloxy-3-methyl-3-butylene, 3-methylene radical-2-(methyl) acryloxy-norbornane, 4, 4 '-ethylene phenol two (methyl) acrylate, methacrolein two (methyl) acryl acetal, p-((methyl) acryl methyl) vinylbenzene, allyl group (methyl) acrylate, 2-(brooethyl) vinylformic acid vinyl, 2-(methylol) vinylformic acid allyl group etc.

Be used to form the monomer of the unit that contains itrile group

The monomer that is used to form the unit that contains itrile group using in this form can be enumerated 2-cyano ethyl vinyl ether, cyano methyl vinyl ether, 3-cyanopropyl vinyl ether, 4-cyano group butyl vinyl ether, 1-(to cyano-benzene oxygen)-2-vinyloxy group-ethane, 1-(adjacent cyano-benzene oxygen)-2-vinyloxy group-ethane, 1-(cyano-benzene oxygen)-2-vinyloxy group-ethane, 1-(to cyano-benzene oxygen)-3-vinyloxy group-propane, 1-(to cyano-benzene oxygen)-4-vinyloxy group-butane, o-cyanobenzyl vinyl ether, between cyano group benzyl vinyl ether, to cyano group benzyl vinyl ether, allyl cyanide compound, allyl group cyano group acetic acid or following compound etc.

[changing 21]

As polymerization process, method or the middle general cationic polymerization of recording of " experimental technique of Polymer Synthesizing " large Tianjin grand row work the 7th chapter (p195) that can use experimental chemistry lecture " polymer chemistry " the 2nd chapter-4 (p74) to record.The example of the initiator that can use in cationoid polymerisation in addition, has protonic acid, halo metal, organometallic compound, organic salt, metal oxide and solid acid, halogen.Wherein, halo metal and organometallic compound, because active large, can synthesize the initiator of high molecular, are preferred.

Object lesson has boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, Tin tetrabromide, phosphorus pentafluoride, ammonium chloride, molybdenum chloride, tungsten chloride, iron(ic) chloride, ethyl aluminum dichloride, chloro diethyl aluminum, dichloromethyl aluminium, Chlorodimethyl aluminium, trimethyl aluminium, trimethylammonium zinc, メチ Le グリニア.

1-2) formation of main polymer chain is radical polymerization, and the polymeric species of the polymerizable group of introducing on side chain is the form of cationoid polymerisation

In the present invention, the formation of main polymer chain is radical polymerization, the polymeric species of the polymerizable group of introducing on side chain be the monomer that uses in the form of cationoid polymerisation can enumerate have a following compound.

Be used to form the monomer of the unit that contains polymerizable group

Can use and above-mentioned 1-1) form in the identical monomer of the monomer that is used to form the unit that contains polymerizable group enumerated.

Be used to form the monomer of the unit that contains itrile group

The example of the monomer that is used to form the unit that contains itrile group using in this form can be enumerated cyano methyl (methyl) acrylate, 2-cyano ethyl (methyl) acrylate, 3-cyanopropyl (methyl) acrylate, 2-cyanopropyl (methyl) acrylate, 1-cyano ethyl (methyl) acrylate, 4-cyano group butyl (methyl) acrylate, 5-cyano group amyl group (methyl) acrylate, 6-cyano group hexyl (methyl) acrylate, 7-cyano group hexyl (methyl) acrylate, 8-cyano group hexyl (methyl) acrylate, 2-cyano ethyl-(3-(brooethyl) acrylate), 2-cyano ethyl-(3-(methylol) acrylate), to cyano-phenyl (methyl) acrylate, adjacent cyano-phenyl (methyl) acrylate, between cyano-phenyl (methyl) acrylate, 5-(methyl) acryl-2-nitrile-norbornylene, 6-(methyl) acryl-2-nitrile-norbornylene, 1-cyano group-1-(methyl) acryl-hexanaphthene, 1,1-dimethyl-1-cyano group-(methyl) acrylate, 1-dimethyl-1-ethyl-1-cyano group-(methyl) acrylate, o-cyanobenzyl (methyl) acrylate, between cyano group benzyl (methyl) acrylate, to cyano group benzyl (methyl) acrylate, 1-cyano group suberyl acrylate, 2-cyano-phenyl acrylate, 3-cyano-phenyl acrylate, Malonic mononitrile vinyl acetate, 1-cyano group-1-cyclopropane carboxylic acid vinyl acetate, Malonic mononitrile allyl group, 1-cyano group-1-cyclopropane-carboxylic acid allyl group, N, N-dicyano methyl (methyl) acrylamide, N-cyano-phenyl (methyl) acrylamide, allyl group cyano group methyl ether, allyl group-adjacent cyano ethyl ether, an allyl group-cyano group benzylic ether, allyl group-to cyano group benzylic ether etc.

And, also can use the monomer of the part structure that for hydrogen, hydroxyl, alkoxyl group, halogen, cyano group etc. replace with above-mentioned monomer.

As polymerization process, can use method or the middle general radical polymerization of recording of " experimental technique of Polymer Synthesizing " large Tianjin grand row work the 5th chapter (p125) in experimental chemistry lecture " polymer chemistry " the 2nd chapter-2 (p34), recorded.In addition, in the initiator of radical polymerization known have must be heated to 100 ℃ of above high-temperature initiators, the normal starter that is heated to 40～100 ℃ of beginnings, the redox initiator starting etc. under utmost point low temperature, from stability, the polyreaction of initiator, easily control consideration, preferably conventional initiator.

As the example of normal starter, that can enumerate has benzoyl peroxide, lauroyl peroxide, peroxidation dithionate, Diisopropyl azodicarboxylate, azo-2, a 4-methyl pentane nitrile.

2) when the formation polymeric species of main polymer chain is identical with the polymeric species of the polymerizable group of introducing on side chain

Form the polymeric species of main polymer chain when identical with the polymeric species of the polymerizable group of introducing on side chain, be divided into 2-1) both cationoid polymerisations, and 2-2) forms of radical polymerization both.

2-1) form of cationoid polymerisation both

Both, in the form of cationoid polymerisation, as the monomer with itrile group, can use and above-mentioned 1-1) form in the identical monomer of the monomer that is used to form the unit that contains itrile group enumerated.

In addition, in order to prevent the gelation in polymerization, pre-synthesis, have after the polymkeric substance of itrile group, make this polymkeric substance and the compound with the polymerizable group of cationically polymerizable (be called aptly " reactive compounds " below.) reaction, preferably the method for the polymerizable group of cationically polymerizable is introduced in use on side chain.

In addition, the polymkeric substance with itrile group for reactive compounds reaction, preferably there is the reactive group shown in following.

And, there is the combination that the polymkeric substance of itrile group and reactive compounds are preferably functional group such below suitable selection.

As the example of concrete combination, that can enumerate has (reactive group of polymkeric substance, the functional group of reactive compounds)=(carboxyl, carboxyl), (carboxyl, epoxy group(ing)), (carboxyl, isocyanate group), (carboxyl, halogeno-benzyl), (hydroxyl, carboxyl), (hydroxyl, epoxy group(ing)), (hydroxyl, isocyanate group), (hydroxyl, halogeno-benzyl) (isocyanate group, hydroxyl), (isocyanate group, a carboxyl) etc.

Here, as the object lesson of reactive compounds, can enumerate have vinyl carbinol, 4-hydroxyl butane-ethylene base ether, 2-hydroxyl ethane vinyl ether, 3-hydroxy propane vinyl ether, hydroxyl triethylene glycol vinyl ether, 1st terpinol, 2-methyl-2-propanol, 3-methyl-3-butanols, 3-methylene radical-2-hydroxyl-norbornane, to (chloromethyl) vinylbenzene.

2-2) both are the form of radical polymerization

Both are the form of radical polymerization, that as synthetic method, can enumerate has an i) there is the monomer of itrile group and there is the method for the monomer copolymerizable of polymerizable group, ii) there is the monomer and the monomer copolymerizable with two key precursors of itrile group, then with processing such as alkali, introduce the method for two keys, iii) there is the polymkeric substance and the monomer reaction with polymerizable group of itrile group, introduce (introducing polymerizable group) method of two keys.From synthetic adaptability, consider, preferred ii) there is the monomer and the monomer copolymerizable with two key precursors of itrile group, then by processing such as alkali, introduce the method for two keys, iii) there is the polymkeric substance and the monomer reaction with polymerizable group of itrile group, introduce the method for polymerizable group.

Above-mentioned i) monomer with polymerizable group using in synthetic method, that can enumerate has allyl group (methyl) acrylate or following compound etc.

[changing 22]

As above-mentioned ii) synthetic method in the monomer with two key precursors that uses, having of can the enumerating compound that following formula (a) represents etc.

[changing 23]

formula (a)

In above-mentioned formula (a), A is the organic group with polymerizable group, R ¹～R ³be respectively hydrogen atom or 1 valency organic group independently, B and C can react the disengaging group of removing by disengaging, and alleged disengaging reaction here refers to by the effect of alkali and sloughs C, or sloughs B.Preferably B is negatively charged ion, and C is positively charged ion.

As the compound representing in formula (a), concrete can enumerate have a following compound.

[changing 24]

[changing 25]

And, at above-mentioned ii) synthetic method in, two key precursors are transformed in two keys, as shown in following, by disengagings, react the method for removing the disengaging group that B, C represent, in other words, use is removed C by the effect of alkali, the reaction of disengaging B.

[changing 26]

As the preferred example of the alkali using in above-mentioned disengaging reaction, the hydride that has basic metal class, oxyhydroxide or carbonate, organic amine compound, the metallic alkoxide compound that can enumerate.The preferred example of the hydride of basic metal class, oxyhydroxide or carbonate has sodium hydride, hydrolith, potassium hydride KH, sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate, saleratus, sodium bicarbonate etc.The preferred example of organic amine compound has Trimethylamine 99, triethylamine, diethylmethyl amine, Tributylamine, tri-isobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylam,ne, N, N-diethyl cyclo-hexylamine, N-methyl bicyclic hexyl amine, N-ethyl dicyclohexylamine, tetramethyleneimine, 1-crassitude, 2, 5-dimethyl pyrrolidine, piperidines, 1-methyl piperidine, 2, 2, 6, 6-tetramethyl piperidine, piperazine, 1, 4-lupetazin, rubane, 1, 4-diaza-bicyclo [2, 2, 2]-octane, vulkacit H, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, lutidine, 1, 8-diaza-bicyclo (5, 4, 0)-7-undecylene (DBU), N, N '-dicyclohexyl carbodiimide (DCC), diisopropylethylamine, Schiff alkali etc.The preferred example of metallic alkoxide compound can be enumerated sodium methoxyl group compound, sodium ethoxylate, potassium tert.-butoxy compound etc.These alkali can be used separately a kind of or two or more mixing.

And, above-mentioned disengaging reaction kind, the example of the solvent using when (interpolation) alkali is provided, that can enumerate has Ethylene Dichloride, pimelinketone, methylethylketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy ethyl acetic ester, 1-methoxy-2-propanol, 1-methoxyl group-2-propyl-acetic acid ester, a N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, vinyl acetic monomer, methyl lactate, ethyl lactate, water etc.These solvents can be separately or two or more mixing.

The amount of the alkali using can be below equivalent with respect to particular functional group's in compound (the disengaging base that B, C represent) amount, and also can be for more than equivalent.And, while using excessive alkali, depart from after reaction, in order to remove remaining alkali, preferably add the forms such as acid.

Above-mentioned iii) polymkeric substance with itrile group using in synthetic method is by above-mentioned 1-2) form in the monomer that is used to form the unit that contains itrile group enumerated and have that to carry out radical polymerization synthetic for introducing the monomer of the reactive group of two keys.

As having for introducing the example of monomer of the reactive group of two keys, having of enumerating has the monomer that has carboxyl, hydroxyl, epoxy group(ing) or isocyanate group that can enumerate as reactive group.

As the example of the monomer that contains carboxyl, that can enumerate has (methyl) vinylformic acid, methylene-succinic acid, a M-nitro benzoic acid vinyl acetate; Synthetic アロニ Network ス M-5300 (Ah Lou Ni Kusi M-5300), M-5400, the M-5600 (being all trade(brand)name) manufacturing in East Asia; Acrylate PA, HH (being all trade(brand)name) that the レ of Mitsubishi mono-シヨ Application (Lay bear) is manufactured; The ライト acrylate HOA-HH (being all trade(brand)name) that common prosperity corporatization length of schooling is made; NK エステ Le SA, A-SA (being all trade(brand)name) etc. that middle village chemistry is manufactured.

Example as the monomer that contains hydroxyl, that can enumerate has 2-hydroxyethyl (methyl) acrylate, 4-hydroxyl butyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate, 1-(methyl) acryl-3-hydroxyl-diamantane, methylol (methyl) acrylamide, 2-(methylol)-(methyl) acrylate, the methyl esters of 2-(methylol)-(methyl) acrylate, the chloro-2-hydroxypropyl of 3-(methyl) acrylate, 3, 5-dihydroxyl amyl group (methyl) acrylate, 1-methylol-4-(methyl) acryl methyl-cyclohexyl alkane, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 1-methyl-2-acryloxy propyl group phthalic acid, 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, 1-methyl-2-acryloxy ethyl-2-hydroxypropyl phthalic acid, 2-acryloxy ethyl-2-hydroxyl-3-chloropropyl phthalic acid, アロニ Network ス M-554 (Ah Lou Ni Kusi M-554), M-154, M-555, M-155, M-158 (being all trade(brand)name) that the synthetic company limited in East Asia manufactures, Block レ Application マ mono-PE-200 (Bu Leimu PE-200), PE-350, PP-500, PP-800, PP-1000,70PEP-350B, 55PET800 (being all trade(brand)name) that Japan grease company limited manufactures, with there is the interior ester modified acrylate of structure below.

CH ₂＝CRCOOCH ₂CH ₂[OC(＝O)C ₅H ₁₀] _nOH

(R=H or methyl, n=1～5)

As the example with the monomer of epoxy group(ing), サイ Network ロマ mono-A, the M (Sa one storehouse Lou nurse A, M) (being all trade(brand)name) etc. that have glycidyl (methyl) acrylate, ダイセ Le (large charity game Shandong) chemistry to manufacture that can enumerate.

As the example with the monomer of isocyanate group, カレ Application ズ A OI (Ka Lanzi AOI), the MOI (being all trade(brand)name) that have clear and electrician to manufacture that can enumerate.

In addition, the polymkeric substance with itrile group using in synthetic method iii) can further contain the 3rd kind of copolymerization composition.

Above-mentioned iii) in synthetic method, can be different according to thering is the kind of reactive group in the polymkeric substance of itrile group from monomer polymer reaction, that there is polymerizable group with itrile group.Can use the monomer with the functional group combining below.

That is that, can enumerate has (reactive group of polymkeric substance, the functional group of monomer)=(carboxyl, carboxyl), (carboxyl, epoxy group(ing)), (carboxyl, isocyanate group), (carboxyl, halogeno-benzyl), (hydroxyl, carboxyl), (hydroxyl, epoxy group(ing)), (hydroxyl, isocyanate group), (hydroxyl, halogeno-benzyl) (isocyanate group, hydroxyl), (isocyanate group, carboxyl), (epoxy group(ing), a carboxyl) etc.

As object lesson, can enumerate monomer below.

[changing 27]

In the polymerizable polymer that contains itrile group of the present invention, the L in above-mentioned formula (1), formula (3) or formula (4) ¹be while having the divalent organic group structure of amino-formate bond, the synthetic method (synthetic method of polymkeric substance of the present invention) shown in preferably using is below synthesized.

The feature of the synthetic method of polymkeric substance of the present invention is at least in solvent, to use on side chain, have the polymkeric substance of hydroxyl and have isocyanate group and the compound of polymerizable group, by add this isocyanate groups on this hydroxyl, forms L ¹in amino-formate bond.

Here, the preferred example on the side chain using in the synthetic method as polymkeric substance of the present invention with the polymkeric substance of hydroxyl, that can enumerate has an above-mentioned 1-2) in the multipolymer of (methyl) acrylate that contains hydroxyl that is used to form the monomer that contains itrile group unit and enumerates below of enumerating.

Example as (methyl) acrylate that contains hydroxyl, that can enumerate has (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, 1-(methyl) acryl-3-hydroxyl-diamantane, methylol (methyl) acrylamide, (methyl) vinylformic acid 2-(methylol)-ester, the methyl esters of 2-(methylol)-(methyl) acrylate, the chloro-2-hydroxypropyl of 3-(methyl) acrylate, 3, 5-dihydroxy pentyl (methyl) acrylate, 1-methylol-4-(methyl) acryl methyl-cyclohexyl alkane, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 1-methyl-2-acryloxy propyl group phthalic acid, 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, 1-methyl-2-acryloxy ethyl-2-hydroxypropyl phthalic acid, 2-acryloxy ethyl-2-hydroxyl-3-chloropropyl phthalic acid, アロニ Network ス M-554 (Ah Lou Ni Kusi M-554), M-154, M-555, M-155, M-158 (being all trade(brand)name) that the synthetic company limited in East Asia manufactures, Block レ Application マ mono-PE-200 (Bu Leimu PE-200), PE-350, PP-500, PP-800, PP-1000,70PEP-350B, 55PET800 (being all trade(brand)name) that Japan grease company limited manufactures, and there is the lactone modification acrylate of structure below.

CH ₂＝CRCOOCH ₂CH ₂[OC(＝O)C ₅H ₁₀] _nOH

(R=H or methyl, n=1～5)

The polymkeric substance on the side chain using in the synthetic method of polymkeric substance of the present invention in addition, with hydroxyl further can contain the 3rd kind of copolymerization composition.

On side chain described above, have in the polymkeric substance of hydroxyl, from synthesizing the viewpoint of the polymkeric substance of high molecular, consider, as raw material, preferably use the raw material of 2 functional acrylates of by-product while having removed synthetic (methyl) acrylate that contains hydroxyl to carry out synthetic polymkeric substance.As refining method, preferably distillation, post are refined.More preferably use (methyl) acrylate that contains hydroxyl that passes through successively following (1)～(4) step acquisition to synthesize.

(1) by comprise (methyl) acrylate that contains hydroxyl and when synthetic (methyl) acrylate that this contains hydroxyl 2 functional acrylates' of by-product mixture be dissolved in the step in water;

(2) in the aqueous solution obtaining, add after the 1st kind of organic solvent separated with water the step of the layer that contains the 1st kind of organic solvent and above-mentioned 2 functional acrylates from water layer separation;

(3) in above-mentioned water layer, dissolve than the step of the above-mentioned water-soluble high compound of (methyl) acrylate that contains hydroxyl;

(4) in above-mentioned water layer, add the 2nd kind of organic solvent, extract after above-mentioned (methyl) acrylate that contains hydroxyl concentrated step.

The mixture using in above-mentioned steps (1) comprise (methyl) acrylate that contains hydroxyl and when synthetic (methyl) acrylate that this contains hydroxyl impurity-2 functional acrylate of by-product, suitable with the general commercially available product of (methyl) acrylate that contains hydroxyl.

In above-mentioned steps (1), in water, dissolve this commercially available product (mixture), obtain the aqueous solution.

In above-mentioned steps (2), the aqueous solution obtaining in step (1) is added to the 1st kind organic solvent separated with water.The example of the 1st kind of organic solvent used herein can be enumerated vinyl acetic monomer, diethyl ether, benzene, toluene etc.

Then, the layer (oil reservoir) that contains the 1st kind of organic solvent and 2 functional acrylates from the aqueous solution (water layer) separation.

In above-mentioned steps (3), in the water layer separated with oil reservoir in step (2), dissolve than the water-soluble high compound of (methyl) acrylate that contains hydroxyl.

The example of the water-soluble high compound of (methyl) acrylate that ratio used herein contains hydroxyl has the inorganic salt such as the alkali earth metal salts such as an alkali metal salts such as sodium-chlor, Repone K, sal epsom, calcium sulfate etc.

In above-mentioned steps (4), in water layer, add the 2nd kind of organic solvent, after (methyl) acrylate that extraction contains hydroxyl, concentrated.

As the example of the 2nd kind of organic solvent used herein, that can enumerate has vinyl acetic monomer, diethyl ether, benzene, a toluene etc.The 2nd kind of organic solvent can be identical with aforesaid the 1st kind of organic solvent, also can be different.

In concentrated in step (4), be with anhydrous magnesium sulfate drying or underpressure distillation etc.

The isolate that comprises (methyl) acrylate that contains hydroxyl that passes through successively above-mentioned steps (1)～(4) acquisition preferably contains 2 functional acrylates of the following scope of 0.1 quality % of its gross weight.In other words, through above-mentioned steps (1)～(4), from mixture, remove impurity 2 functional acrylates, refining (methyl) acrylate that contains hydroxyl.

The preferred content range of 2 functional acrylate is below 0.05 quality % of isolate gross weight, more few better.

Use refining like this (methyl) acrylate that contains hydroxyl, because impurity 2 functional acrylates are difficult to affect polyreaction, can synthesize weight-average molecular weight is more than 20000 polymerizable polymers that contains itrile group.

As (methyl) acrylate that contains hydroxyl using in above-mentioned steps (1), on the side chain using in the synthetic method that has the invention described above polymkeric substance that can enumerate, there is (methyl) acrylate that contains hydroxyl that the polymkeric substance of hydroxyl is used when synthetic.Wherein, from the reactivity with isocyanic ester, consider, preferably there is the monomer of primary hydroxyl, further, from improving the ratio of the polymerizable group of the every unit weight of polymkeric substance, consider (methyl) acrylate that contains hydroxyl that preferred molecular weight is 100～250.

And, the compound with isocyanate group and polymerizable group using in synthetic method as polymkeric substance of the present invention, that can enumerate has 2-acryloxy ethyl isocyanate (trade(brand)name: カレ Application ズ AOI (Ka Lanzi AOI) ,Zhao He electrician company limited manufacture), a 2-methacryloxy isocyanic ester (trade(brand)name: カレ Application ズ MOI (Ka Lanzi MOI) ,Zhao He electrician company limited manufactures) etc.

And, the solvent using in the synthetic method as polymkeric substance of the present invention, preferably SP value (Gen Ju Red Tianjin method is calculated) be 20～23MPa ^1/2concrete can enumerate have glycol diacetate, Diethylene Glycol diacetate esters, propylene-glycol diacetate, methyl acetoacetate, an ethyl 3-oxobutanoate, 1; 2; 3-triacetoxyl group-propane, pimelinketone, 2-(1-tetrahydrobenzene) pimelinketone, propionitrile, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, Acetyl Acetone, methyl phenyl ketone, triacetin, Isosorbide-5-Nitrae-dioxs, dimethyl carbonate etc.

Wherein, from synthetic high molecular body, consider, more preferably ester series solvent, particularly preferably diacetate esters series solvent or the dimethyl carbonate such as glycol diacetate, Diethylene Glycol diacetate esters.

Here, pretty straight work " the Japanese bonding association magazine " 29 (3) (1993) in method (Red Tianjin, SP value Shi Gen Ju Red Tianjin of solvent in the present invention) calculate.Concrete, SP value is calculated according to following formula.In addition, Δ F is the value that document is recorded.

SP value (δ)=∑ Δ F (mole attraction constant)/V (molecular volume)

As all with respect to copolymerization composition in the above-mentioned synthetic polymerizable polymer that contains itrile group of the present invention, the unit that contains polymerizable group, the ratio of unit preferably in scope below that contains itrile group.

That is, the unit containing polymerizable group preferably accounts for 5 all～50mol% of copolymerization composition, more preferably 5～40mol%.Words reactive (hardening, polymerizability) below 5mol% reduce, and easy gelation when the words more than 50mol% are synthesized, is difficult to synthesize.

And, the unit that contains itrile group, from the adsorptivity of plating catalyst etc. is considered, preferably the scope with the 5～95mol% all with respect to copolymerization composition contains, and more preferably the scope with 10～95mol% contains.

In addition, the polymerizable polymer that contains itrile group of the present invention except the unit that contains itrile group, contain polymerizable group unit, can contain other unit.As the monomer that is used to form other unit uses, as long as in the scope of harmless effect of the present invention, can use any monomer.

When aforesaid polymerizable group is introduced in reaction in polymkeric substance, while being difficult to 100% introducing, because residual a small amount of reactive part, have the possibility of the 3rd kind of unit.

As being used to form the above-mentioned unit that contains itrile group, the object lesson of the monomer that other unit are used beyond the unit that contains polymerizable group, that can enumerate has (methyl) ethyl propenoate while forming main polymer chain in radical polymerization, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, unsubstituted (methyl) esters of acrylic acids such as (methyl) vinylformic acid stearyl, (methyl) vinylformic acid 2,2,2-trifluoroethyl ester, (methyl) vinylformic acid 3,3,3-trifluoro propyl ester, (methyl) esters of acrylic acid that the halogens such as (methyl) vinylformic acid 2-chloro-ethyl ester replace, (methyl) esters of acrylic acid that the ammoniums such as 2-(methyl) acrylyl oxy-ethyl-trimethyl ammonium muriate replace, butyl (methyl) acrylamide, sec.-propyl (methyl) acrylamide, octyl group (methyl) acrylamide, (methyl) acrylic amides such as dimethyl (methyl) acrylamide, vinylbenzene, vinyl M-nitro benzoic acid, the styrenics such as p-vinyl puratized agricultural spray muriate, N-vinylcarbazole, vinyl acetate, N-vinyl acetamide, vinyl compound class or other dimethyl aminoethyls (methyl) acrylate such as N-caprolactam, diethylamino ethyl (methyl) acrylate, 2-ethylenebis dithiocarbamate ethyl (methyl) acrylate, (methyl) vinylformic acid, 2-hydroxyethyl (methyl) acrylate etc.

And, use the macromole of the monomer acquisition of above-mentioned record to use.

While forming main polymer chain by cationoid polymerisation, the vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, IVE, cyclohexyl vinyl ether, ethylene glycol vinyl ether, two (ethylene glycol) vinyl ether, BDO vinyl ether, 2-chloroethyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxy group tetrahydropyrans, vinyl benzoic acid ester, vinyl butyrate, vinylbenzene, to chloro-styrene, to end vinyl such as the styrenics such as methoxy styrene, vinyl carbinol, 4-hydroxyl-1-butenes.

The weight-average molecular weight of the polymerizable polymer that contains itrile group of the present invention is preferably more than 1000, below 700,000, more preferably more than 2000, below 200,000.From polymerization sensitivity, consider especially, the weight-average molecular weight of the polymerizable polymer that contains itrile group of the present invention is preferably more than 20000.

And, as the polymerization degree of the polymerizable polymer that contains itrile group of the present invention, preferably use 10 products more than repeating unit, more preferably 20 products more than repeating unit.And, preferably 7000 below repeating unit, more preferably 3000 below repeating unit, more preferably 2000 below repeating unit, particularly preferably 1000 below repeating unit.

The object lesson of the polymerizable polymer that contains itrile group of the present invention is expressed as follows, but is not limited to these examples.

In addition, the weight-average molecular weight of these object lessons is one of any all in 3000～100000 scope.

[changing 28]

Form 1-1) polymkeric substance obtaining in

[changing 29]

Form 1-2) polymkeric substance obtaining in

[changing 30]

Form 2-1) polymkeric substance obtaining in

[changing 31]

Form 2-2) polymkeric substance obtaining in

[changing 32]

Form 2-2) polymkeric substance obtaining in

[changing 33]

Form 2-2) polymkeric substance obtaining in

[changing 34]

Form 2-2) polymkeric substance obtaining in

Here, for example the compound 2-2-11 of above-mentioned object lesson is dissolved in vinylformic acid and 2-cyanoethyl acrylate for example in N-Methyl pyrrolidone, what be used as polymerization starter carries out radical polymerization as azo isobutyronitrile (AI BN), then, use the such catalyzer of benzyl triethyl ammonium ammonium muriate, under the state of the polymerization retarder that interpolation tertiarybutylhydroquinone is such, addition polymerization glycidyl methacrylate thing synthesizes.

And, for example the compound 2-2-19 of above-mentioned object lesson is dissolved in the such solvent of N, N-DMAA by monomer below with to cyano group benzyl acrylate, use the such polymerization starter of azo isopropylformic acid dimethyl ester, carry out radical polymerization, then, with the such alkali of triethylamine, carrying out desalination acid synthesizes.

[changing 35]

The polymerizable polymer that contains itrile group of the present invention for example adds in the basic solution of pH12, and being decomposed in the situation below 50% of polymerizable group position while stirring 1 hour, can clean with high alkalinity solution this polymkeric substance.

The use form of novel polymer of the present invention

The polymerizable polymer that contains itrile group of the present invention is because be to have itrile group unit and the multipolymer with the unit of polymerizable group, changes and under the ratio of unit, can control plating catalyst etc. to the adsorptivity of metal and polymerizability (reactivity).

The such polymerizable polymer that contains itrile group of the present invention can be for except Photocurable resin composition, in the electronic applications of formed material, coating material, surface modifying material, material for substrate, mechanical field, field of food, building field, automotive field.

In various uses, no matter have or not hydrophobicity, to the adsorptivity of plating catalyst and the good consideration of polymerizability, the polymerizable polymer that contains itrile group of the present invention is preferably used as the finish materials that forms electroplating film.

For example, the polymerizable polymer that contains itrile group of the present invention use surface grafting polymerization method etc. directly Chemical bond to the base material of expectation, can improve and the adaptation of base material, good to the adsorptivity of plating catalyst, and then can form the polymer layer that water-absorbent is few.On this polymer layer, provide plating catalyst, then, when applying electroplating film that electroplating processes forms because keeping good adaptation with polymer layer, polymer layer is difficult to keep moisture or ion etc., also has the effect of the variation of the temperature can't see, humidity dependence or shape.

Especially, while using the base material that forms this electroplating film in the manufactures such as electrical harnesses, can play the good effect of wiring closet insulation reliability.

In addition, in the base material that forms electroplating film, preferably use the resin base material that contains epoxy resin, polyimide resin or P ET resin.

In addition, the polymerizable polymer that contains itrile group of the present invention can be used the composition for example, mixing with other compositions (solvent).Now, the content of the polymerizable polymer that contains itrile group of the present invention is preferably the scope of 2 quality %～50 quality %, the more preferably scope of 5 quality %～30 quality % with respect to the gross weight of said composition.

The solvent using in the composition that contains the polymerizable polymer that contains itrile group of the present invention so long as can dissolve this polymkeric substance, is not particularly limited.And, in solvent, can further add tensio-active agent.

The object lesson of the solvent that can use with there is the composition of the compound (polymerizable polymer that for example contain cyano group) of above-mentioned polymerizable group with interaction group in the object lesson of the solvent that can use the same, its applicable object lesson is too.And various conditions when the various conditions when composition that contains the polymerizable polymer that contains itrile group of the present invention is applicable to be coated with purposes (conditions such as the temperature of composition, the concentration of each composition, additive) are also coated with the composition of the above-mentioned polymerizable polymer that contains cyano group are the same.

The base material that the composition of the polymerizable polymer that use contains nitrile group-containing of the present invention is used while forming multilayer body, the flap of dimensional stabilizing, can meet according to the suitable selection of application target the product of certain folding property, intensity, weather resistance etc. thus.

Concrete, such as the product that has the moulding such as polyimide resin, bimaleimide resin, polyphenylene oxide resin, epoxy resin, liquid crystalline polymers, teflon resin that can enumerate, or the paper of paper, metal sheet (such as aluminium, zinc, copper etc.), lamination or the above-mentioned metal of evaporation of polysiloxane substrate, paper, stratified plastics or plastics film etc.

In addition, as mentioned above, use the polymerizable polymer contain itrile group on base material, to form electroplating film, while this electroplating film being applicable in the manufacture of diet wiring board, the product that preferably uses insulative resin to make as base material.

[embodiment]

Below, by embodiment, illustrate in greater detail the present invention, but the invention is not restricted to this.In addition, do not specify, " % " " partly (part) " take quality as benchmark.

Embodiment 1-1

The manufacture of substrate

On glass epoxy substrate, heating and pressurizing is as the epoxy insulating film GX-13 (trade(brand)name of aginomoto Off アイ Application テ Network ノ (aginomoto fine chemistry) the company manufacture of electric insulation layer, thickness: 45 μ m), by vacuum laminator, under the pressure of 0.2MPa, the condition of 100 ℃～110 ℃, engage, obtain base material.

Then, on base material, by spin-coating method coating thickness, be the insulativity composition that contains polymerization starter of the following composition of 3 microns, at 30 ℃, place 1 hour, except after desolventizing, at 140 ℃, be dried 30 minutes, form polymerization trigger layer (the polymerization trigger layer of insulativity).

The insulativity composition that contains polymerization starter

By bisphenol A type epoxy resin (epoxy equivalent (weight): 185, oiling Shell epoxy company limited manufactures, trade(brand)name: エピコ mono-ト 828 (a Chinese mugwort mouth throws 828)) 20 mass parts, cresol-novolak type epoxy resin (epoxy equivalent (weight) 215, large Japanese ink chemical industry company limited manufactures, trade(brand)name: エピ Network ロ Application N-673 (Ai Biku dragon N-673)) 45 mass parts, phenol aldehyde resin (phenolic hydroxyl group equivalent 105, large Japanese ink chemical industry company limited manufactures, trade(brand)name: Off エノライト (throwing of Fu Ainong Rye)) 30 mass parts add in 20 parts of ethyl ethyl glycol acetates and 20 parts of solvent oils, heating for dissolving while stirring, after cool to room temperature, now add pimelinketone wax (the oiling Shell epoxy company limited manufacture of the phenoxy resin of above-mentioned エピコ mono-ト 828 (a Chinese mugwort mouth throws 828) and bisphenol S formation, trade(brand)name: YL674 7H30, nonvolatile component 30 quality %, weight-average molecular weight 47000) 30 mass parts, 2-phenyl-4, two (methylol) imidazoles 0.8 weight parts of 5-, Crushing of Ultrafine silicon-dioxide 2 mass parts, silicon is defoamer 0.5 mass parts, in this mixture, add again 10 parts of polymerization initiated polymerization thing P that following method is synthetic, the insulativity composition that acquisition contains polymerization starter.

Polymerization initiated polymerization thing P's is synthetic

The propylene glycol monomethyl ether (MFG) that adds 30g in the three-necked flask of 300ml, is heated to 75 degree.Then, in 2.5 hours, drip 8.1g[2-(acryloxy) ethyl] (4-phenoxy benzyl) dimethyl brometo de amonio and 9.9g HEMA, 13.5g methacrylic acid isopropyl esters, 0.43g dimethyl-2, the solution of 2 '-azo two (2 Methylpropionic acid ester), 30g MF G.Then, temperature of reaction is elevated to 80 degree, further reacts 2 hours, obtain the polymer P with polymerization initiating radical.

Form after above-mentioned polymerization trigger layer, at 180 ℃, implement 30 minutes solidification treatment.Thus, obtain substrate A1.The concave-convex surface (Rz) of this substrate A1 is 0.2 μ m.

The formation of polymer layer

Polymer A synthetic with polymerizable group and interaction group

First, as described below, the synthetic polymer A with polymerizable group and interaction group.

In the three-necked flask of 1000ml, add 35g N,N-dimethylacetamide, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip 6.60g2-hydroxy ethyl methacrylate (commercially available product, Tokyo changes into manufacture), the solution of the 35g N,N-dimethylacetamide of 28.4g2-vinylformic acid cyano ethyl ester, 0.65g azo two methyl isobutyrates (trade(brand)name: V-601, and the pure medicine manufacture of light).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.29g ditert-butylhydro quinone, 0.29g dibutyltin dilaurate, 18.56g カレ Application ズ AOI (Ka Lanzi AOI) (trade(brand)name, the manufacture of Zhao He electrician company limited), 19g N, N-N,N-DIMETHYLACETAMIDE reacts 4 hours at 55 ℃.Then, add 3.6g methyl alcohol in reaction solution, z reacts 1.5 hours again.After reaction terminating, with the vinyl acetic monomer-hexane of 1: 1, carry out redeposition, take out solids, obtain the polymer A (weight-average molecular weight 1.5 ten thousand) that 32g has polymerizable group and interaction group.

The preparation of coating solution

Polymer A, 73.3 mass parts acetone, 33.9 mass parts methyl alcohol and the 4.8 mass parts N 10.5 mass parts to polymerizable group and interaction group, N N,N-DIMETHYLACETAMIDE mix and blend, prepares coating solution.

The generation of graftomer

By the coating solution of preparation, by spin-coating method, the thickness with 1 μ m is applied on the polymerization trigger layer of aforesaid substrate A1, dry after 30 minutes at 80 ℃, the use three UV exposure machines that motor is manufactured forever (trade(brand)name: UVF-502S, lamp: UXM-501MD), with 1.5mW/cm ²irradiation power (the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UIT150) and photo-sensitive cell (trade(brand)name: UVD-S254) mensuration) irradiate 660 seconds, generate graftomer on the whole surface of the polymerization trigger layer of substrate A1.Here, cumulative exposure amount is 990m J.

Then, under the state stirring, in acetone, dipping generates the substrate 5 minutes of graftomer, then with distilled water, cleans.

Thus, obtain the substrate A2 with polymer layer.

The physical property measurement of polymer layer

The physical property of the polymer layer obtaining is measured with aforesaid method.Result is expressed as follows.

Saturated water absorption under 25 ℃ of-50% relative humidity environment: 1.2 quality %

Saturated water absorption under 25 ℃ of-95% relative humidity environment: 3.4 quality %

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 7.5 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 70.3 degree

Providing of plating catalyst

The substrate A2 with polymer layer, flooding after 30 minutes containing in the acetone soln of 1% Palladous nitrate, is flooded in acetone, clean.

Then, use the mixing solutions of 1% dimethylaminoborane-water/methyl alcohol (water/methyl alcohol=1/3) as catalyst activity liquid (reduced liquid), the substrate A2 with polymer layer is flooded after 15 minutes in this solution, in acetone, flood, clean.

Electroless plating

As mentioned above, to thering is the substrate A2 of the polymer layer that plating catalyst is provided, use the electroless plating of following composition to bathe, at 60 ℃, carry out 5 minutes electroless platings.The thickness of the electrolytic copper free electroplating film obtaining is 0.3 μ m.

The composition that electroless plating is bathed

The pH of the plating bath forming is above adjusted to 12.5 (60 ℃) with sodium hydroxide and sulfuric acid.

Metallide

Then,, using electrolytic copper free electroplating film as giving electricity layer, use the electrolytic copper plating bath of following composition, at 3A/dm ²condition under carry out metallide 20 minutes.The thickness of the copper electroplating film obtaining is 18 μ m.

The composition that metallide is bathed

Adaptation is evaluated

To the electroplating film obtaining, use tensile testing machine (エ of company limited mono-ア Application De デ mono-(Ai Ang struggle against Di) manufacture, trade(brand)name: RTM-100), under 5mm width, carrying out the mensuration of 90 ° of stripping strengths with tensile strength 10mm/min, is 0.7kN/mm.

The formation of metal pattern and the test of insulation reliability

On the electroplating film surface obtaining, forming etch-resistant coating on the region of kish model (Wiring pattern), there is no the electroplating film FeCl in the region of resist layer ₃the etching solution that/HCl makes is removed.Then, the alkaline stripping liquid that etch-resistant coating makes with 3%NaOH liquid is removed, and is formed for measuring the comb shape distribution (metal pattern material) of reliability of insulating between the line of line and interval=100 μ m/100 μ m.

To HAST trier (trade(brand)name: AMI-150S-25 for this comb shape distribution, ESP EC manufactures) the relative humidity (unsaturation) of 125 ℃-85%, apply under voltage 10V, 2 normal atmosphere and place 200 hours, do not find the defective insulation of wiring closet.

Embodiment 1-2

Use the substrate A1 manufacturing in embodiment 1-1, form polymerization trigger layer, manufacture such surface metal mould material below.

The formation of polymer layer

Polymer B synthetic with polymerizable group and interaction group

First, as described below, the synthetic polymer B with polymerizable group and interaction group.

In the three-necked flask of 1000ml, add 42g N,N-dimethylacetamide, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip 5.6g HEA (commercially available product, Tokyo changes into manufacture), the solution of the 42g N,N-dimethylacetamide of 36.1g vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, 0.55g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, cooled reaction solution is to room temperature.

In above-mentioned reaction soln, add 0.24g ditert-butylhydro quinone, 0.30g dibutyltin dilaurate, 15.5g カレ Application ズ AOI (Ka Lanzi AOI) (trade(brand)name, the manufacture of Zhao He electrician company limited), 16g N, N-N,N-DIMETHYLACETAMIDE reacts 4 hours at 55 ℃.Then, in reaction solution, add 3.1g methyl alcohol, then react 1.5 hours.After reaction terminating, with distilled water, carry out redeposition, take out solids, obtain the polymer B (weight-average molecular weight 1.7 ten thousand) that 30g has polymerizable group and interaction group.

The preparation of coating solution

Polymer B, 73.3 mass parts Virahols, 33.9 mass parts methyl alcohol and the 4.8 mass parts N 7.9 mass parts to polymerizable group and interaction group, N N,N-DIMETHYLACETAMIDE mix and blend, prepares coating solution.

The generation of graftomer

By the coating solution of preparation, with spinner, by spin-coating method, the thickness with 1 μ m is applied on the polymerization trigger layer of aforesaid substrate A1, dry after 30 minutes at 80 ℃, the use three UV exposure machines that motor is manufactured forever (trade(brand)name: UVF-502S, lamp: UXM-501MD), at 1.5mW/cm ²irradiation power (the lower irradiation of the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UI T150) and photo-sensitive cell (trade(brand)name: UVD-S254) measure)) 660 seconds generates graftomer on the whole surface of polymerization trigger layer of substrate A1.Here, cumulative exposure amount is 990mJ.

Then, in the methyl alcohol of whipped state, dipping generates the substrate 5 minutes of graftomer, then with distilled water, cleans.

Thus, obtain the substrate A3 with polymer layer.

The physical property measurement of polymer layer

Physical property to the polymer layer obtaining is measured with aforesaid method.Result is expressed as follows.

Saturated water absorption under 25 ℃ of-50% relative humidity environment: 0.8 quality %

Saturated water absorption under 25 ℃ of-95% relative humidity environment: 3.0 quality %

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 5.5 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 83.9 degree

Then, to thering is the substrate A3 of this polymer layer, use the method the same with embodiment 1-1, the providing of plating catalyst, electroless plating and metallide are provided.

Adaptation is evaluated

To the electroplating film obtaining, use tensile testing machine (エ of company limited mono-ア Application De デ mono-(Ai Ang struggle against Di) manufacture, trade(brand)name: RTM-100), under 5mm width, with the tensile strength of 10mm/m in, carrying out the mensuration of 90 ° of stripping strengths, is 0.67kN/mm.

The formation of metal pattern and the test of insulation reliability

On the electroplating film surface obtaining, forming etch-resistant coating on the region of kish model (Wiring pattern), there is no the electroplating film FeCl in the region of resist layer ₃the etching solution that/HCl makes is removed.Then, etch-resistant coating is removed with the alkaline stripping liquid that 3%NaOH liquid forms, and is formed for measuring the comb shape distribution (metal pattern material) of reliability of insulating between the line of line and interval=100 μ m/100 μ m.

To this comb shape distribution, use ESPEC to manufacture HAST trier (trade(brand)name: AMI-150S-25) under 125 ℃ of-85% relative humidity (unsaturation), place 200 hours applying under voltage 10V, 2 normal atmosphere, do not find the defective insulation of wiring closet.

Embodiment 1-3

The manufacture of substrate

On the base material that Kapton (trade(brand)name: カプト Application 500H (the same 500H of Kapp) ,Dong Li E.I.Du Pont Company manufactures) forms, use No. 18 rods to be coated with following polymerization trigger layer coating fluid, at 110 ℃, be dried 10 minutes, carry out crosslinking reaction.The thickness of the polymerization trigger layer obtaining is 9.3 μ m.The substrate obtaining is like this as substrate B1.The concave-convex surface (Rz) of the substrate B1 obtaining is 0.3 μ m.

Polymerization trigger layer coating fluid

Above-mentioned polymerization initiated polymerization thing P 0.4g

TDI (benzyl support-2,4-vulcabond) 0.16g

Methylethylketone (MEK) 1.6g

The formation of polymer layer

The preparation of coating solution

By above-mentioned polymer A, 73.3 mass parts methylethylketones (MEK), 33.9 mass parts methyl alcohol and the 4.8 mass parts N with polymerizable group and interaction group of 10.5 mass parts, N N,N-DIMETHYLACETAMIDE mix and blend, prepares coating solution.

The generation of graftomer

After the coating solution of preparation is used the method the same with embodiment 1-1 to be spin-coated on the polymerization trigger layer of aforesaid substrate B1, dry, use UV exposure machine (trade(brand)name: UVF-502S, lamp: UXM-501MD, three motor manufactures forever), at 1.5mW/cm ²irradiation power (the lower irradiation of the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UIT150) and photo-sensitive cell (trade(brand)name: UVD-S254) measure)) 800 seconds generates graftomer on the whole surface of the polymerization trigger layer of substrate B1.Here, cumulative exposure amount is 1200mJ.

Then, in the acetone under whipped state, dipping has generated the substrate 5 minutes of graftomer, then, with distilled water, cleans.

Thus, obtain the substrate B2 with polymer layer.

The physical property measurement of polymer layer

Saturated water absorption under 25 ℃ of-50% relative humidity environment: 1.4 quality %

Saturated water absorption under 25 ℃ of-95% relative humidity environment: 3.9 quality %

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 7.8 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 72.6 degree

Then, to thering is the substrate B2 of this polymer layer, use the method the same with embodiment 1-1, the providing of plating catalyst, electroless plating and metallide are provided.

Adaptation is evaluated

Electroplating film to obtaining, is used the method evaluation adaptation the same with embodiment 1-1, and 90 ° of stripping strengths are 0.68kN/mm.

The formation of metal pattern and the test of insulation reliability

To as the substrate with electroplating film of above-mentioned acquisition, use the method the same with embodiment 1-1, form comb type distribution (metal pattern material), the reliability that insulate is tested, and does not find the defective insulation of wiring closet.

Embodiment 1-4

The manufacture of substrate

There is the カプト Application EN (the same EN of Kapp) (manufacture of trade(brand)name ，Dong Li Dupont Co., Ltd) of 25 μ m thickness as base material.The saturated water absorption of this base material under 25 ℃ of-50% relative humidity is 1.0 quality %.

On the two sides of this base material (resin film), use infusion method to be coated with the insualtion resin composition that polymerization causes energy that has of following composition, dry after 5 minutes at 100 ℃, 250 ℃ of heating 30 minutes, form polymerization trigger layer (the polymerization trigger layer of insulativity).In addition, the saturated water absorption of polymerization trigger layer under 25 ℃ of-50% relative humidity is 1.2 quality %.

Using the substrate obtaining as substrate C1.The concave-convex surface of this substrate C1 is as (Ra), and the Ra based on ISO4288 (1996), is used サ mono-Off コ system (Sa Fu kowtows order) 3000A (trade(brand)name, the accurate company limited in Tokyo manufactures) to measure, and is 0.1 μ m.

Contain the insulativity composition that polymerization causes energy

Synthesizing of polyimide precursor (polyamic acid)

Under nitrogen, in N-Methyl pyrrolidone (30ml), dissolve 4,4 '-diamino-phenyl ether (5.75g:28.7mmol), at room temperature stir about is 30 minutes.In this solution, add 3,3 ', 4,4 at 0 ℃ "-benzophenone tetracarboxylic dianhydride (9.25g:28.7mmo l), stirs 5 hours.Redeposition reaction solution, obtains and contains the polyimide precursor (polyamic acid) that polymerization causes energy.According to the molecular weight of GPC (gel permeation chromatography) (Mw), be 2.8 ten thousand.And, further pass through ¹h-NMR, FT-IR confirm its structure.

The polyimide precursor obtaining is dissolved in N,N-dimethylacetamide (manufacture of DMAc ,He Guangchun medicine company limited), prepares the solution of 10 quality %.

The formation of polymer layer

The preparation of coating solution

By above-mentioned polymer A, 73.3 mass parts methylethylketones (MEK), 33.9 mass parts methyl alcohol and the 4.8 mass parts N,N-dimethylacetamide mix and blends with polymerizable group and interaction group of 10.5 mass parts, prepare coating solution.

The generation of graftomer

Use infusion method with the thickness of 1 μ m, to be coated on the polymerization trigger layer on two sides of aforesaid substrate C1 the coating solution of preparation, dry after 30 minutes at 80 ℃, the use three UV exposure machines that motor is manufactured forever (trade(brand)name: UVF-502S, lamp: UXM-501MD), at 1.5mW/cm ²irradiation power (the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UIT150) and under photo-sensitive cell (trade(brand)name: UVD-S254) mensuration)), irradiated for 660 seconds, on the polymerization trigger layer of substrate C1, generate graftomer.Here, cumulative exposure amount is 990m J.

Thus, obtain on two sides and there is the substrate C2 that thickness is the polymer layer of 0.8 μ m.

The physical property measurement of polymer layer

Providing of plating catalyst

The substrate C2 with polymer layer, flooding after 30 minutes containing in the acetone soln of 1% Palladous nitrate, is flooded in acetone, clean.

Then, in the mixing solutions of 1% dimethylaminoborane-water/methyl alcohol (water/methyl alcohol=1/3), the substrate B2 dipping with polymer layer, after 15 minutes, is flooded in acetone, clean.

Electroless plating

As aforesaid way, to thering is the substrate C2 of the polymer layer that plating catalyst is provided, use the electroless plating the same with above-described embodiment 1-1 to bathe, at 60 ℃, carry out the electroless plating of 5 minutes.The thickness of the electrolytic copper free electroplating film on the two sides obtaining is 0.3 μ m.

Metallide

Then,, using electrolytic copper free electroplating film as giving electricity layer, use the electrolytic copper plating bath that form the same as above-described embodiment 1-1, at 3A/dm ²condition under, metallide 20 minutes.The thickness of the electrolytic copper electroplating film on the two sides obtaining is 18 μ m.

Adaptation is evaluated

To the electroplating film obtaining, the same with embodiment 1-1, under 5mm width, with the tensile strength of 10mm/mi n, carry out the mensuration of 90 ° of stripping strengths, be 0.68kN/m.

The formation of metal pattern and the test of insulation reliability

To as the substrate with electroplating film of above-mentioned acquisition, use the method the same with embodiment 1-1, form comb type distribution (metal pattern).

Then, use this comb type distribution, use the method the same with embodiment 1-1, the reliability that insulate is tested, and does not find the defective insulation of wiring closet.

Embodiment 1-5

In embodiment 1-1, the polymkeric substance C with polymerizable group and interaction group that the polymer A with polymerizable group and interaction group of using while forming polymer layer is synthesized in the following method replaces, and then conditions of exposure changes to 10mW/cm ²irradiation power under irradiate beyond 100 seconds, the same with embodiment 1-1, form polymer layer.Here, cumulative exposure amount is 1000mJ.

Thus, obtain the substrate A4 with polymer layer.

In addition, while forming polymer layer, even be under 500mJ in cumulative exposure amount, also obviously can form the same polymer layer.

Polymkeric substance C synthetic with polymerizable group and interaction group

The commercially available product of 200mL hydroxy ethyl methacrylate (Tokyo changes into company limited and manufactures) is dissolved in 600mL water.In the aqueous solution obtaining, add 400mL vinyl acetic monomer, separated oil reservoir.Then, in water layer, dissolve 100g sodium-chlor (manufacture of He Guangchun medicine company limited), then, use 200m L vinyl acetic monomer to carry out 2 extractions.Then, extract anhydrous magnesium sulfate drying, adds 0.04g to methoxyl group Resorcinol, and vinyl acetic monomer is heated up in a steamer in appropriateness decompression.After decompression is heated up in a steamer, with NMR, confirm, vinyl acetic monomer remaining quantity is 6.5 quality %.

And the content with 2 functional acrylates in liquid phase chromatography (HPLC) mensuration hydroxy ethyl methacrylate commercially available product, is 0.28 quality %, but measures above-mentioned refining like this product, 2 functional acrylates' content is for detecting below boundary.

Refining hydroxy ethyl methacrylate, the 10.01g vinylformic acid cyano ethyl ester of N-Methyl pyrrolidone, 2.32g aforesaid method that adds 20mL in the three-necked flask of 500mL, be warmed up to 75 ℃, wherein the mixed solution of 0.23g V-601 (aforementioned) and 5mL N-Methyl pyrrolidone dripped in 1 hour.Drip and stop, after latter 1 hour, being warmed up to 80 ℃, react 1 hour.

In above-mentioned reaction soln, add 0.29g ditert-butylhydro quinone, 0.29g dibutyltin dilaurate, 18.56g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ，Zhao He electrician company limited) and 19g N-Methyl pyrrolidone (SP value: 22.94MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 3.6g methyl alcohol, and then react 1.5 hours.After reaction terminating, water redeposition, takes out solids, obtains the polymkeric substance C that 25g has polymerizable group and interaction group.

The evaluation of structure

In heavy DMSO (dimethyl sulfoxide (DMSO)), dissolve the synthetic polymkeric substance C with polymerizable group and interaction group, under the NMR of 300MHz (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufactures), measure.Suitable peak is that 4.3-4.05p pm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak under (3H divides) with containing cyano group unit, the peak suitable with the unit that contains polymerizable group is that 7.2-7.3pp m (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=20 of containing cyano group: 80 (mol ratios).

The mensuration of molecular weight

The synthetic polymkeric substance C with polymerizable group and interaction group is dissolved in tetrahydrofuran (THF) (TH F), uses high speed GPC (trade(brand)name, HLC-8220GPC, eastern ソ mono-manufactures) to carry out the mensuration of molecular weight.As a result, at 23.75 minutes, there is being converted into polystyrene in peak Mw=22000 (Mw/Mn=2.1).

The physical property measurement of polymer layer

Saturated water absorption under 25 ℃ of-50% relative humidity environment: 1.3 quality %

Saturated water absorption under 25 ℃ of-95% relative humidity environment: 3.5 quality %

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 8.3 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 71.6 degree

Then, to thering is the substrate A4 of this polymer layer, use the method the same with embodiment 1-1, the providing of plating catalyst, electroless plating and metallide are provided.And then, at 170 ℃, carry out the post-heating of 30 minutes.

Adaptation is evaluated

Electroplating film to obtaining, is used the method evaluation adaptation the same with embodiment 1-1, and 90 ° of stripping strengths are 0.75kN/mm.

The formation of metal pattern and the test of insulation reliability

As the substrate with electroplating film of above-mentioned acquisition, use the method the same with embodiment 1-1, form comb type distribution (metal pattern material), the reliability that insulate is tested, and does not find the defective insulation of wiring closet.

Embodiment 1-6

In embodiment 1-1, the polymer A with polymerizable group and interaction group of using during by formation polymer layer replaces to the polymkeric substance D with polymerizable group and interaction group that method is synthesized below, and then conditions of exposure changes over 10mW/cm ²irradiation power under irradiate beyond 100 seconds, the same with embodiment 1-1, form polymer layer.Here, cumulative exposure amount is 1000mJ.

Thus, obtain the substrate A5 with polymer layer.

In addition, while forming polymer layer, even when cumulative exposure amount is 500mJ, also can form the same polymer layer.

Polymkeric substance D synthetic with polymerizable group and interaction group

In the three-necked flask of 500mL, add 11mL glycol diacetate, be warmed up to 75 ℃, in 2.5 hours, drip wherein the mixed solution with the glycol diacetate of the method for embodiment 1-5 record refining 1.39g hydroxy ethyl methacrylate, 6.00g vinylformic acid cyano ethyl ester, 0.1382g V-601 (aforementioned) and 11mL.Drip after termination, be warmed up to 80 ℃, react 3 hours.

In above-mentioned reaction soln, add 0.06g ditert-butylhydro quinone, 0.13g inorganic bismuth urethane crosslinking catalyst (trade(brand)name: ネオスタ Application U-600 (Nai Ousi hall U-600), day east changes into manufacture), 3.84g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 3.8g glycol diacetate (SP value: 20.79MPa ^1/2), at 55 ℃, carry out reaction in 6 hours.

Then, in reaction solution, add 3.6g methyl alcohol, and then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the polymkeric substance D that 3g has polymerizable group and interaction group.

The evaluation of structure

The synthetic polymkeric substance D with polymerizable group and interaction group is dissolved in heavy DMSO (dimethyl sulfoxide (DMSO)), under the NMR of 300MHz (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture), measures.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak under (3H divides), suitable peak is that 7.2-7.3p pm (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=21 of containing itrile group: 79 (mol ratios) with containing polymerizable group unit.

The mensuration of molecular weight

The synthetic polymkeric substance D with polymerizable group and interaction group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result occurred being converted into polystyrene in peak at 23.75 minutes, Mw=84000 (Mw/Mn=2.9).

The physical property measurement of polymer layer

Saturated water absorption under 25 ℃ of-95% relative humidity environment: 3.6 quality %

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 7.7 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 70.8 degree

Then, to thering is the substrate A5 of this polymer layer, use the method the same with embodiment 1-1, the providing of plating catalyst, electroless plating and metallide are provided.And then, at 170 ℃, carry out the post-heating of 30 minutes.

Adaptation is evaluated

Electroplating film to obtaining, is used the method evaluation adaptation the same with embodiment 1-1, and 90 ° of stripping strengths are 0.76kN/mm.

The formation of metal pattern and the test of insulation reliability

To as substrate above-mentioned acquisition, that there is electroplating film, use the method the same with embodiment 1-1, form comb type distribution (metal pattern material), the reliability that insulate is tested, and does not find the defective insulation of wiring closet.

Embodiment 1-7

In embodiment 1-1, the polymer A with polymerizable group and interaction group of using during by formation polymer layer replaces to the polymkeric substance E with polymerizable group and interaction group that method is synthesized below, and then conditions of exposure is changed over 10mW/cm ²irradiation power irradiate beyond 100 seconds, the same with embodiment 1-1, form polymer layer.Here, cumulative exposure amount is 1000mJ.

Thus, obtain the substrate A6 with polymer layer.

Polymkeric substance E synthetic with polymerizable group and interaction group

In the three-necked flask of 500mL, add 10mL glycol diacetate, be warmed up to 80 ℃, in 4 hours, drip therein the mixed solution with refining 3.72g hydroxy ethyl methacrylate, 16.01g vinylformic acid cyano ethyl ester, 0.3684g V-601 (aforementioned) and 10mL glycol diacetate of the method for embodiment 1-5 record.Drip after termination, then react 3 hours.

In above-mentioned reaction soln, add 0.16g ditert-butylhydro quinone, 0.32g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 9.6g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 9.6g glycol diacetate (SP value: 20.79MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 3.6g methyl alcohol, and then react again 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the polymkeric substance E that 18g has polymerizable group and interaction group.

The evaluation of structure

To synthetic polymkeric substance E carry out NMR the same as the embodiment 1-2 mensuration with polymerizable group and interaction group, the unit that contains polymerizable group: unit=23 of containing itrile group: 77 (mol ratios).

The mensuration of molecular weight

The synthetic polymkeric substance E with polymerizable group and interaction group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture), carry out the mensuration of molecular weight.Result occurred being converted into polystyrene in peak at 23.75 minutes, Mw=66000 (M w/Mn=2.8).

The physical property measurement of polymer layer

In 100 ℃ of boiling water, flood the water-intake rate after 1 hour: 8.1 quality %

Under 25 ℃ of-50% relative humidity environment, drip 5 μ L distilled water, the surface contact angle after standing 15 seconds: 70.0 degree

Then, to thering is the substrate A6 of this polymer layer, use the method the same with embodiment 1-1, the providing of plating catalyst, electroless plating and metallide are provided.And then at 170 ℃, carry out the post-heating of 30 minutes.

Adaptation is evaluated

Electroplating film to obtaining, is used the method the same with embodiment 1-1, evaluates adaptation, and 90 ° of stripping strengths are 0.76kN/mm.

The formation of metal pattern and the test of insulation reliability

Embodiment 1-8

With the substrate A1 manufacturing in embodiment 1-1, formed polymerization trigger layer, as following manner is manufactured metal pattern material.

The formation of polymer layer

The same with embodiment 1-1, use the polymer A with polymerizable group and interaction group to prepare coating solution.

The pattern of graftomer forms

The coating solution of preparation is used to spinner, and with spin-coating method, the thickness with 1 μ m is applied on the polymerization trigger layer of aforesaid substrate A1, dry after 5 minutes at 80 ℃, the use three UV exposure machines that motor is manufactured forever (trade(brand)name: UVF-502S, lamp: UXM-501MD), at 10mW/cm ²irradiation power (100 seconds of the lower irradiation of the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UIT150) and photo-sensitive cell (trade(brand)name: UVD-S254) measure)).Now, be coated with on substrate A1 dry after coating solution, the pattern of placing wide 5mm, long 50mm is the mask A of 0.1mm spacing parallel arranging or the mask B of line and interval=100 μ m/100 μ m comb type distribution, expose, the graftomer of pattern generation shape on the polymerization trigger layer of substrate A1.Here, cumulative exposure amount is 1000mJ.

Then, in the acetonitrile under whipped state, flood the substrate that generates graftomer in 5 minutes, then, with distilled water, clean.

Thus, under the pattern form of wide 5mm, long 50mm, acquisition has the substrate A7 that thickness is the polymer layer of 0.5 μ m (using mask A), A8 (using mask B).

The physical property measurement of polymer layer

Each physical property of the polymer layer obtaining is the same with embodiment 1-1.

Providing of plating catalyst

There is the substrate A7 of polymer layer flooding after 30 minutes containing in the acetone soln of 0.1 quality % Palladous nitrate, in acetone, flood, clean.

Electroless plating

As mentioned above, to the substrate A7 with polymer layer of plating catalyst is provided, use the electroless plating of following composition to bathe, at 60 ℃, carry out the electroless plating of 15 minutes.The thickness of the electrolytic copper free electroplating film obtaining is 0.50 μ m.

The composition that electroless plating is bathed

Metallide

Then,, using electrolytic copper free electroplating film as giving electricity layer, use the method the same with embodiment 1-1, the electrolytic copper electroplating film that electroplating thickness is 18 μ m on substrate A7, electroplating thickness is 10 μ m on substrate A8.

Metallide carries out 30 minutes after stopping at 100 ℃, carries out the roasting of 1 hour at 170 ℃.

Adaptation is evaluated

To as the metal pattern electroplating film of the substrate A7 of above-mentioned acquisition, use tensile testing machine (エ of company limited mono-ア Application De デ mono-(Ai Ang struggle against Di) manufacture, RTM-100), with the tensile strength of 10mm/m in, carrying out the mensuration of 90 ° of stripping strengths, is 0.65kN/mm.

The test of insulation reliability

To as the metal pattern of the substrate A8 of above-mentioned acquisition, the method based on embodiment 1-1, the reliability that insulate test, does not find the defective insulation of wiring closet (between metal pattern).

Embodiment 2-1

Synthesis example: the polymerizable polymer A's that contains itrile group of the present invention is synthetic

In the three-necked flask of 1000ml, add 35g N-Methyl pyrrolidone, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the 35g N-Methyl pyrrolidone solution of 6.60g2-hydroxy ethyl methacrylate (commercially available product, Tokyo changes into manufacture), 28.4g2-vinylformic acid cyano ethyl ester and 0.65g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, and then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.29g ditert-butylhydro quinone, 0.29g dibutyltin dilaurate, 18.56g カレ Application ズ AOI (Ka Lanzi AOI) (trade(brand)name, Zhao He electrician company limited manufactures) and 19g N-Methyl pyrrolidone, at 55 ℃, react 6 hours.Then, in reaction solution, add 3.6g methyl alcohol, and then react 1.5 hours.After reaction terminating, water redeposition, takes out solids, obtains the 25g polymerizable polymer A that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer A that contains itrile group is dissolved in heavy DMSO, measures the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.2-7.3ppm (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=23 of containing itrile group: 77 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer A that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was found peak at 23.75 minutes, was converted into polystyrene, Mw=5300 (Mw/Mn=1.54).

The use form of the polymerizable polymer A that contains itrile group

On glass epoxy substrate, heat, pressurize as the epoxy insulating film (trade(brand)name: G X-13 of electric insulation layer, aginomoto Off アイヲテ Network ノ (aginomoto fine chemistry) company manufactures, thickness: 45 μ m), bonding under the pressure of 0.2MPa, the condition of 100 ℃～110 ℃ by vacuum laminator, obtain base material A.

Then,, on base material A, use spin-coating method with the thickness of 3 μ m, to be coated with the insulativity composition of the polymerization starter that contains following composition, at 30 ℃, place 1 hour, except after desolventizing, at 140 ℃, be dried 30 minutes, form polymerization trigger layer (the polymerization trigger layer of insulativity).

The insulativity composition that contains polymerization starter

By the aqueous bisphenol A type epoxy resin of 5g (epoxy equivalent (weight) 176, japan epoxy resin company limited manufactures, trade(brand)name: エピコ mono-ト 825 (a Chinese mugwort mouth throws 825)), (large Japanese ink chemical industry company limited manufactures the MEK wax of the resol that 2g contains triazine structure, trade(brand)name: Off エノライト LA-7052, nonvolatile component: 62%, the phenolic hydroxyl group equivalent of nonvolatile component: 120), (Dongdu changes into company limited and manufactures 10.7g phenoxy resin MEK wax, trade(brand)name: YP-50EK35, nonvolatile component: 35%), 2.3g is as 2-hydroxyl-4 '-(2-the hydroxyl-oxethyl)-2-methyl phenyl ketone of polymerization starter, 5.3g MEK, 0.053g2-ethyl-4-methylimidazole mix and blend, it is dissolved completely, the insulativity composition that acquisition contains polymerization starter.

As above form after polymerization trigger layer, at 180 ℃, implement the solidification treatment of 30 minutes.Thus, obtain substrate A1.The concave-convex surface (Rz) of this substrate A1 is 0.2 μ m.

The preparation of coating solution

The 10.5 weight parts polymerizable polymer A that contains itrile group of the present invention, 73.3 weight part acetone, 33.9 weight part methyl alcohol and the 4.8 weight part N that in aforesaid synthesis example, obtain, N N,N-DIMETHYLACETAMIDE mix and blend, prepares coating solution.

Exposure

By the coating solution of preparation, by spin-coating method, the thickness with 1 μ m is coated on the polymerization trigger layer of aforesaid substrate A1, dry after 30 minutes at 80 ℃, the use three UV exposure machines that motor is manufactured forever (trade(brand)name: UVF-502S, lamp: UXM-501MD), at 1.5mW/cm ²irradiation power (the lower irradiation of the ultraviolet accumulated light meter of manufacturing with ウシオ (Ouchy Europe) motor (trade(brand)name: UIT150) and photo-sensitive cell (trade(brand)name: UVD-S254) measure)) 660 seconds reacts the polymerizable polymer A that contains itrile group on the whole surface of the polymerization trigger layer of substrate A1.

Then, the substrate that has formed photocurable layers is flooded 5 minutes in the acetone under whipped state, then, with distilled water, clean.

Thus, obtain the substrate A2 with polymer layer.

Providing of plating catalyst

The substrate A2 with polymer layer, flooding after 30 minutes containing in the acetone soln of 1%Pd, is flooded in acetone, clean.

Then, the mixing solutions of 1% dimethylaminoborane-water/methyl alcohol (water/methyl alcohol=1/3), as catalyst activity liquid (reduced liquid), is flooded the substrate A2 with polymer layer after 15 minutes in this solution, dipping acetone, cleans.

Electroless plating

The composition that electroless plating is bathed

Metallide

Then,, using electrolytic copper free electroplating film as giving electricity layer, use the electrolytic copper plating bath of following composition, at 3A/dm ²condition under electroplate 20 minutes.Then, calcination process 1 hour at 120 ℃.The thickness of the electroplating copper film obtaining is 18 μ m.

The composition that metallide is bathed

The formation of metal pattern and the test of insulation reliability

On the electroplating film surface obtaining, in region that should kish model (Wiring pattern), form etch-resistant coating, there is no the electroplating film FeCl in the region of resist layer ₃the etching solution that/HCl forms is removed.Then, etch-resistant coating is removed with the alkaline stripping liquid that 3%NaOH liquid forms, and with welding resist, covers, and is formed for measuring the comb shape distribution (metal pattern material) of reliability of insulating between the line of line and interval=100 μ m/100 μ m.

This comb shape distribution with ESPEC manufacture HAST trier (AMI-150S-25) 125 ℃ of-85% relative humidity (unsaturation), apply under voltage 10V, 2 normal atmosphere and place 200 hours, do not find the defective insulation of wiring closet.

Embodiment 2-2

Synthesis example: the polymerizable polymer B's that contains itrile group of the present invention is synthetic

200mL hydroxy ethyl methacrylate (commercially available product, Tokyo change into manufacture) is dissolved in 600mL water.In the aqueous solution obtaining, add 400mL vinyl acetic monomer, separated oil reservoir.Then, in water layer, dissolve 100g sodium-chlor (manufacture of He Guangchun medicine company limited), then, use 200mL vinyl acetic monomer to carry out 2 extractions.Then, extract anhydrous magnesium sulfate drying, adds 0.04g to methoxyl group Resorcinol, and vinyl acetic monomer is heated up in a steamer in appropriateness decompression.After decompression is heated up in a steamer, with NMR, confirm the vinyl acetic monomer of remaining 6.5 quality %.

And, with the 2 functional acrylic ester contents that vapor-phase chromatography (GC) is measured in hydroxy ethyl methacrylate commercially available product, being 0.28 quality %, but measuring as above-mentioned refining goods, 2 functional acrylates' content is detecting below boundary.

In the three-necked flask of 500mL, add 20mL N-Methyl pyrrolidone, the refining hydroxy ethyl methacrylate of aforesaid method, 10.01g vinylformic acid cyano ethyl ester for 2.32g, be warmed up to 75 ℃, in 1 hour, drip wherein the mixed solution of 0.23g V-601 (aforementioned) and 5mL N-Methyl pyrrolidone.Drip and stop latter 1 hour, be warmed up to 80 ℃, react 1 hour.

In above-mentioned reaction soln, add 0.29g ditert-butylhydro quinone, 0.29g dibutyltin dilaurate, 18.56g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 19g N-Methyl pyrrolidone, at 55 ℃, react 6 hours.Then, in reaction solution, add 3.6g methyl alcohol, and then react 1.5 hours.After reaction terminating, water redeposition, takes out solids, obtains the 25g polymerizable polymer B that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer B that contains itrile group is dissolved in heavy DMSO (dimethyl sulfoxide (DMSO)), with the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz, measures.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.2-7.3ppm (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=20 of containing itrile group: 80 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer B that contains itrile group is dissolved in THF, with high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture), carries out the mensuration of molecular weight.As a result, at 23.75 minutes, there is being converted into polystyrene in peak Mw=22000 (Mw/Mn=2.1).

The use form of the polymerizable polymer B that contains itrile group

Except using as the above-mentioned synthetic polymerizable polymer B that contains itrile group, all prepare composition the same as embodiment 2-1, is used its to form multilayer body, manufactures comb shape distribution (metal pattern material).

The comb shape distribution obtaining is carried out to the test the same with embodiment 2-1, do not find the defective insulation of wiring closet.

Embodiment 2-3

Synthesis example: the polymerizable polymer C's that contains itrile group of the present invention is synthetic

In the three-necked flask of 500mL, add 11mL glycol diacetate, be warmed up to 75 ℃, in 2.5 hours, drip wherein the mixed solution of refining hydroxy ethyl methacrylate, 6.00g vinylformic acid cyano ethyl ester, 0.1382g V-601 (aforementioned) and 11mL glycol diacetate of the method for embodiment 2-2 record for 1.39g.Drip after termination, be warmed up to 80 ℃, react 3 hours.

In above-mentioned reaction soln, add 0.06g ditert-butylhydro quinone, 0.13g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 3.84g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited), 3.8g glycol diacetate (SP value: 20.79MPa ^1/2), at 55 ℃, react 6 hours.

Then, in reaction solution, add 3.6g methyl alcohol, and then react again 1.5 hours.After reaction terminating, water redeposition, takes out solids, obtains the 3g polymerizable polymer C that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer C that contains itrile group is dissolved in heavy DMSO (dimethyl sulfoxide (DMSO)), with the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz, measures.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.2-7.3ppm (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=21 of containing itrile group: 79 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer C that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) determining molecular weight.Result was observed peak at 23.75 minutes, was converted into polystyrene, Mw=84000 (Mw/Mn=2.9).

The use form of the polymerizable polymer C that contains itrile group

Except using as the above-mentioned synthetic polymerizable polymer C that contains itrile group, all prepare composition the same as embodiment 2-1, is used its to form multilayer body, manufactures comb shape distribution (metal pattern material).

Comb shape distribution to obtaining, carries out the same test with embodiment 2-1, does not find the defective insulation of wiring closet.

Embodiment 2-4

Synthesis example: the polymerizable polymer D's that contains itrile group of the present invention is synthetic

In the three-necked flask of 500mL, add 30mL Diethylene Glycol diacetate esters, be warmed up to 75 ℃, in 2.5 hours, drip wherein the mixed solution of refining hydroxy ethyl methacrylate, 16.01g vinylformic acid cyano ethyl ester, 0.0737g V-601 (aforementioned) and 30mL Diethylene Glycol diacetate esters of the method for embodiment 2-2 record for 3.72g.Drip after termination, be warmed up to 80 ℃, react 3 hours.

In above-mentioned reaction soln, add 0.16g ditert-butylhydro quinone, 0.32g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 9.6g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 9.6g Diethylene Glycol diacetate esters (SP value: 20.75MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 3.6g methyl alcohol, and then react again 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 18g polymerizable polymer D that contains itrile group of the present invention.

The evaluation of structure

By the synthetic polymerizable polymer D that contains itrile group carry out NMR mensuration the same as embodiment 2-2, the unit that contains polymerizable group: unit=23 of containing itrile group: 77 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer D that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) determining molecular weight.Result was observed peak at 23.75 minutes, was converted into polystyrene, Mw=93000 (Mw/Mn=3.2).

The use form of the polymerizable polymer D that contains itrile group

Except using as the above-mentioned synthetic polymerizable polymer D that contains itrile group, all prepare composition the same as embodiment 2-1, is used its to form multilayer body, manufactures comb shape distribution (metal pattern material).

To the comb shape distribution obtaining, test the same with embodiment 2-1, does not find the defective insulation of wiring closet.

Embodiment 2-5～2-13

Embodiment 2-5～2-13 is according to the synthesis example shown in below, the synthetic polymerizable polymer E～M that contains itrile group of the present invention.

Synthesis example: the polymerizable polymer E's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 29g Diethylene Glycol diacetate esters, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the solution that 3.72g passes through the 30g Diethylene Glycol diacetate esters of 2-hydroxy ethyl methacrylate, 16.01g2-vinylformic acid cyano ethyl ester and the 0.1842g V-601 (aforementioned) refining with embodiment 2-2 mono-quadrat method.Drip after termination, be heated to 80 ℃, and then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.16g ditert-butylhydro quinone, 0.31g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), in 10.28g Diethylene Glycol diacetate esters (SP value: 20.75MPa ^1/2) in dissolved the reaction soln of 10.28g カレ Application ズ MOI (Ka Lanzi MOI) (manufacture of trade(brand)name ,Zhao He electrician company limited), at 55 ℃, react 6 hours.Then, in reaction solution, add 2.05g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 18g polymerizable polymer E that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer E that contains itrile group is dissolved in heavy DMSO, with the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz, measures.The peak suitable with the unit that contains itrile group is that 4.3-4.0ppm (2H divides), 2.9-2.75p pm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.4-7.0ppm (1H divides), 6.1-6.0pp m (1H divides), 5.7-5.6ppm (1H divides), 4.3-4.0ppm (6H divides), 3.4-3.2ppm (2H divides), 2.5-1.3ppm (3H divides), 1.9-1.8ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=22 of containing itrile group: 78 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer E that contains itrile group is dissolved in THF, with high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) determining molecular weight.Result was observed peak at 20.11 minutes, was converted into polystyrene, Mw=78000 (Mw/Mn=3.11).

Synthesis example: the polymerizable polymer F's that contains itrile group of the present invention is synthetic

In the three-necked flask of 1000ml, add 35g N,N-dimethylacetamide, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the solution of 35g N,N-dimethylacetamide of monomer, 24.82g2-vinylformic acid cyano ethyl ester and the 0.5710g V-601 (aforementioned) of the following structure of 10.25g.Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, under ice-cold, add 0.427g4-hydroxyl テ Application Port, 12.54g triethylamine and 315.6g N,N-dimethylacetamide, at room temperature react 4 hours.After reaction terminating, with Virahol: normal hexane=1: 3 carry out redeposition, take out solids, obtain the 24g polymerizable polymer F that contains itrile group of the present invention.

[changing 36]

The evaluation of structure

The synthetic polymerizable polymer F that contains itrile group is dissolved in heavy DMSO, with the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz, measures.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8p pm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.2-7.3ppm (1H divides), 6.4-6.3pp m (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.4-4.05ppm (4H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=23 of containing itrile group: 77 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer F that contains itrile group is dissolved in THF, with high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture), carries out the mensuration of molecular weight.Result was observed peak at 22.47 minutes, was converted into polystyrene, Mw=12000 (Mw/Mn=1.78).

Synthesis example: the polymerizable polymer G's that contains itrile group of the present invention is synthetic

In the three-necked flask of 500mL, add 40g N,N-dimethylacetamide, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the solution of the 40g N,N-dimethylacetamide of 5.04g vinylformic acid, 35.03g2-vinylformic acid cyano ethyl ester and 0.8059g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, under room temperature, add 0.04g ditert-butylhydro quinone, 3.19g triethyl benzyl ammonia chloride, 25.52g サイ Network ロマ mono-A (Sa one storehouse Lou nurse A) (aforementioned), at 100 ℃, react 5 hours.After reaction terminating, with vinyl acetic monomer: normal hexane=2: 3 carry out redeposition, take out solids, obtain the 30g polymerizable polymer G that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer G that contains itrile group is dissolved in to heavy DMSO, with the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz, measures.The peak suitable with the unit that contains itrile group is that 4.4-4.2ppm (2H divides), 3.0-2.8ppm (2H divides), 2.6-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.6-7.5ppm (1H divides), 6.5-6.3ppm (1H divides), 6.3-6.1ppm (1H divides), 6.0-5.8ppm (1H divides), 4.9-4.7 (1H divides), 4.2-4.0 (2H divides), 4.0-3.7 (1H divides), 2.7-1.3ppm observe broad peak in (10H divides), the unit that contains polymerizable group: unit=35 of containing itrile group: 65 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer G that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 22.23 minutes, was converted into polystyrene, Mw=23000 (Mw/Mn=2.17).

Synthesis example: the polymerizable polymer H's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 21g Diethylene Glycol diacetate esters, under nitrogen gas stream, be heated to 75 ℃.Now in 2.5 hours, drip 2.69g and adopt 2-hydroxy ethyl methacrylate, the 17.37g vinylformic acid solution to the 20g Diethylene Glycol diacetate esters of cyano group benzyl ester and 0.0534g V-601 (aforementioned) refining with embodiment 2-2 mono-quadrat method.Drip after termination, stir 2 hours post-heating to 80 ℃, then stir 2 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.12g ditert-butylhydro quinone, 0.23g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 7.09g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 27.09g Diethylene Glycol diacetate esters (SP value: 20.75MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 1.48g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 21g polymerizable polymer H that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer H that contains itrile group is dissolved in heavy DMSO, uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z to measure.The peak suitable with the unit that contains itrile group is that 7.8-7.65ppm (2H divides), 7.5-7.3ppm (2H divides), 5.2-4.9ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.4-7.0ppm (1H divides), 6.4-6.2ppm (1H divides), 6.2-6.0ppm (1H divides), 6.0-5.8ppm (1H divides), 4.2-3.9ppm (6H divides), 3.4-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=23 of containing itrile group: 77 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer H that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 19.85 minutes, was converted into polystyrene, Mw=149000 (Mw/Mn=4.46).

Synthesis example: the polymerizable polymer I's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 20g Diethylene Glycol diacetate esters, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the solution of the 20g Diethylene Glycol diacetate esters of 3.77g employing and embodiment 2-2 mono-quadrat method refining HEMA, 16.15g methacrylic acid 2-cyano ethyl ester and 0.0668g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.15g ditert-butylhydro quinone, 0.29g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 8.82g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 27.82g Diethylene Glycol diacetate esters (SP value: 20.75MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 1.86g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 10g polymerizable polymer I that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer I that contains itrile group is dissolved in heavy DMSO, uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z to measure.The peak suitable with the unit that contains itrile group is that 4.25-4.0ppm (2H divides), 2.95-2.8ppm (2H divides), 2.1-0.5ppm observe broad peak in (5H divides), the peak suitable with the unit that contains polymerizable group is that 7.4-7.0ppm (1H divides), 6.5-6.3ppm (1H divides), 6.3-6.0ppm (1H divides), 6.0-5.8p pm (1H divides), 4.2-3.9ppm (6H divides), 3.5-3.3ppm (2H divides), 2.1-0.5ppm observe broad peak in (5H divides), the unit that contains polymerizable group: unit=24 of containing itrile group: 76 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer I that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 18.52 minutes, was converted into polystyrene, Mw=238000 (Mw/Mn=2.56).

Synthesis example: the polymerizable polymer J's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 33g Diethylene Glycol diacetate esters, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the solution that 4.16g adopts the 33g Diethylene Glycol diacetate esters of HEMA, 17.80g2-cyano ethyl methacrylic ester and the 0.1842g V-601 (aforementioned) refining with embodiment 2-2 mono-quadrat method.Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.16g ditert-butylhydro quinone, 0.32g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 10.66g カレ Application ズ MOI (Ka Lanzi MOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 10.66g Diethylene Glycol diacetate esters (SP value: 20.75MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 2.05g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 20g polymerizable polymer J that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer J that contains itrile group is dissolved in heavy DMSO, uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z to measure.The peak suitable with the unit that contains itrile group is that 4.2-3.95ppm (2H divides), 2.9-2.75ppm (2H divides), 2.1-0.6ppm observe broad peak in (5H divides), the peak suitable with the unit that contains polymerizable group is that 7.4-7.0ppm (1H divides), 6.1-6.0ppm (1H divides), 5.7-5.6ppm (1H divides), 4.2-3.95ppm (6H divides), 3.35-3.2ppm (2H divides), 2.1-0.6ppm observe broad peak in (8H divides), the unit that contains polymerizable group: unit=24 of containing itrile group: 76 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer J that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 19.90 minutes, was converted into polystyrene, Mw=90000 (Mw/Mn=2.45).

Synthesis example: the polymerizable polymer K's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 5g METHYLPYRROLIDONE under nitrogen gas stream, to be heated to 75 ℃.Now, in 2.5 hours, drip 0.53g and adopt 2-hydroxy ethyl methacrylate, the 3.85g2 refining with embodiment 2-2 mono-quadrat method, the 4g solution of the METHYLPYRROLIDONE of 2-diethyl-4-cyano group-ethyl propylene acid esters, 0.0530g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.02g ditert-butylhydro quinone, 0.05g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 1.53g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 1.53g N-methyl-2-Pyrrolidone (SP value: 22.94MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 0.29g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 1g polymerizable polymer K that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer K that contains itrile group is dissolved in heavy DMSO, uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z to measure.The peak suitable with the unit that contains itrile group is 3.9-3.65ppm (2H divides), 2.5-2.3ppm (2H divides), 1.7-1.4ppm (2H divides), 1.4-1.1ppm (4H divides), 0.9-0.6ppm (6H divides), 2.5-1.3ppm observes broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is 7.4-7.0ppm (1H divides), 6.4-6.3ppm (1H divides), 6.3-6.1ppm (1H divides), 6.0-5.9 (1H divides), 4.2-4.0ppm (6H divides), 3.4-3.2ppm (2H divides), 2.0-1.3ppm observes broad peak in (3H divides), the unit that contains polymerizable group: unit=25 of containing itrile group: 75 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer K that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 23.07 minutes, was converted into polystyrene, Mw=6900 (Mw/Mn=1.45).

Synthesis example: the polymerizable polymer L's that contains itrile group of the present invention is synthetic

In the three-necked flask of 300ml, add 25g METHYLPYRROLIDONE, under nitrogen gas stream, be heated to 75 ℃.Now, in 2.5 hours, drip the 25g solution that 3.17g adopts the METHYLPYRROLIDONE of the 2-hydroxy ethyl methacrylate refining with embodiment 2-2 mono-quadrat method, 15.37g2-vinylformic acid cyano ethyl ester, 6.52g vinyl cyanide, 0.6286g V-601 (aforementioned).Drip after termination, be heated to 80 ℃, then stir 3 hours.Then, by reaction soln cool to room temperature.

In above-mentioned reaction soln, add 0.14g ditert-butylhydro quinone, 0.28g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 8.54g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited) and 8.54g METHYLPYRROLIDONE (SP value: 22.94MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 1.75g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 18g polymerizable polymer L that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer L that contains itrile group is dissolved in heavy DMSO, uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MH z to measure.The peak suitable with vinylformic acid cyano ethyl ester units is 4.3-4.0ppm (2H divides), 3.0-2.8ppm (2H divides), 2.7-1.4ppm observes broad peak in (3H divides), the peak suitable with acrylonitrile unit is to observe broad peak in 2.7-1.4ppm (3H divides), the peak suitable with the unit that contains polymerizable group is 7.4-7.0ppm (1H divides), 6.4-6.3ppm (1H divides), 6.3-6.1ppm (1H divides), 6.0-5.9 (1H divides), 4.2-4.0ppm (6H divides), 3.3-3.2ppm (2H divides), 2.7-1.4ppm observes broad peak in (3H divides), the unit that contains polymerizable group: vinylformic acid cyano ethyl ester units: acrylonitrile unit=12: 47: 41 (mol ratio).

The mensuration of molecular weight

The synthetic polymerizable polymer L that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 24.18 minutes, was converted into polystyrene, Mw=4700 (Mw/Mn=1.69).

Synthesis example: the polymerizable polymer M's that contains itrile group of the present invention is synthetic

In the three-necked flask of 500mL, add 10mL dimethyl carbonate, be warmed up to 65 ℃, in 2.5 hours, drip wherein the mixed solution of refining hydroxy ethyl methacrylate, 16.01g vinylformic acid cyano ethyl ester, 0.3974g V-65 and 10m L dimethyl carbonate of the method for embodiment 2-2 record for 3.72g.Drip after termination, add 25mL dimethyl carbonate, then react 3 hours at 65 ℃.After reaction terminating, add 14mL dimethyl carbonate.

In above-mentioned reaction soln, add 0.15g ditert-butylhydro quinone, 0.38g ネオスタ Application U-600 (Nai Ousi hall U-600) (aforementioned), 11.6g カレ Application ズ AOI (Ka Lanzi AOI) (manufacture of trade(brand)name ,Zhao He electrician company limited), 11.6g dimethyl carbonate (SP value: 22.9MPa ^1/2), at 55 ℃, react 6 hours.Then, in reaction solution, add 1.9g methyl alcohol, then react 1.5 hours.After reaction terminating, water carries out redeposition, takes out solids, obtains the 12g polymerizable polymer M that contains itrile group of the present invention.

The evaluation of structure

The synthetic polymerizable polymer M that contains itrile group is dissolved in heavy DMSO (dimethyl sulfoxide (DMSO)), uses the NMR (trade(brand)name: AV-300, Block Le カ mono-(Bu Luka) manufacture) of 300MHz to measure.The peak suitable with the unit that contains itrile group is that 4.3-4.05ppm (2H divides), 2.9-2.8ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the peak suitable with the unit that contains polymerizable group is that 7.2-7.3ppm (1H divides), 6.4-6.3ppm (1H divides), 6.2-6.1ppm (1H divides), 6.0-5.9ppm (1H divides), 4.3-4.05ppm (6H divides), 3.3-3.2ppm (2H divides), 2.5-1.3ppm observe broad peak in (3H divides), the unit that contains polymerizable group: unit=25 of containing itrile group: 75 (mol ratios).

The mensuration of molecular weight

The synthetic polymerizable polymer M that contains itrile group is dissolved in THF, uses high speed GPC (trade(brand)name: HLC-8220GPC, eastern ソ mono-manufacture) to carry out the mensuration of molecular weight.Result was observed peak at 20.40 minutes, was converted into polystyrene, Mw=83000 (Mw/Mn=2.6).

Claims

1. polymkeric substance, wherein, contains the unit that unit that following formula (1) represents and following formula (2) represent:

In formula (1) and formula (2),

represent independently respectively hydrogen atom or replacement or unsubstituted alkyl; X, Y and Z represent respectively singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether independently; L ¹and L ²represent independently respectively to replace or unsubstituted divalent organic group.

2. the polymkeric substance of recording in claim 1, wherein, the unit being represented by above-mentioned formula (1) is the unit being represented by following formula (3):

In formula (3), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl; Z represents singly-bound, replacement or unsubstituted divalent organic group, ester group, amide group or ether; W represents Sauerstoffatom or NR, and R represents hydrogen atom or alkyl here; And L ¹represent to replace or unsubstituted divalent organic group.

3. the polymkeric substance of recording in claim 2, wherein, the unit being represented by above-mentioned formula (3) is the unit being represented by following formula (4):

In formula (4), R ¹and R ²represent independently respectively hydrogen atom or replacement or unsubstituted alkyl; V and W represent respectively Sauerstoffatom or N R independently, and R represents hydrogen atom or alkyl here; And L ¹represent to replace or unsubstituted divalent organic group.

4. the polymkeric substance of recording in claim 3, wherein, in above-mentioned formula (4), W is Sauerstoffatom.

5. the polymkeric substance of recording in claim 1, wherein, the L in above-mentioned formula (1) ¹it is the divalent organic group with amino-formate bond or urea key.

6. the polymkeric substance of recording in claim 1, wherein, the L in above-mentioned formula (1) ¹for total carbon atom number is

divalent organic group.

7. the polymkeric substance of recording in claim 1, wherein, the unit being represented by above-mentioned formula (2) is the unit being represented by following formula (5):

In formula (5), R ⁵represent hydrogen atom or replacement or unsubstituted alkyl; U represents Sauerstoffatom or NR ', and R ' represents hydrogen atom or alkyl here; And L ²represent to replace or unsubstituted divalent organic group.

8. the polymkeric substance of recording in claim 7, wherein, the L in above-mentioned formula (5) ²in the position linking with cyano group be the divalent organic group with the alkylidene group of straight chain, branching or ring-type.

9. the polymkeric substance of recording in claim 8, wherein, the total carbon atom number of above-mentioned divalent organic group is

.

10. the polymkeric substance of recording in claim 7, wherein, L in above-mentioned formula (5) ²in the bond sites with cyano group be the divalent organic group with aromatic group.

The polymkeric substance of recording in 11. claims 10, wherein, the total carbon atom number of above-mentioned divalent organic group is

.

The polymkeric substance of recording in 12. claims 7, wherein, R in above-mentioned formula (5) ⁵for hydrogen atom.

The polymkeric substance of recording in 13. claims 1, wherein, the L in above-mentioned formula (1) ¹it is the divalent organic group with amino-formate bond.

The polymkeric substance of recording in 14. claims 1, wherein, weight-average molecular weight is more than 20,000.

The synthetic method of 15. polymkeric substance, it is the synthetic method of the polymkeric substance of record in claim 13, wherein, comprise at least in solvent, use the polymkeric substance on side chain with hydroxyl and the compound with isocyanate group and polymerizable group, by this isocyanate group of addition on this hydroxyl, form above-mentioned L ¹in the step of amino-formate bond.

The synthetic method of the polymkeric substance of recording in 16. claims 15, wherein, the polymkeric substance on above-mentioned side chain with hydroxyl be use pass through successively following

the synthetic product of (methyl) acrylate that contains hydroxyl that step obtains:

(1) step that 2 functional acrylates' of by-product mixture dissolves in water when comprising (methyl) acrylate of containing hydroxyl and synthetic (methyl) acrylate that contains this hydroxyl

(2) in the aqueous solution obtaining, add after the 1st organic solvent separated with water the step of the separated layer that contains the 1st organic solvent and above-mentioned 2 functional acrylates from water layer

(3) in above-mentioned water layer, dissolve the step of the compound higher than (methyl) acrylate water-soluble that contains above-mentioned hydroxyl

(4) in above-mentioned water layer, add the 2nd organic solvent, extract after above-mentioned (methyl) acrylate that contains hydroxyl concentrated step.

The synthetic method of the polymkeric substance of recording in 17. claims 16, wherein, comprise pass through successively above-mentioned the isolate of (methyl) acrylate that contains hydroxyl of obtaining of step, in its gross weight, contain more than 0 quality % above-mentioned 2 functional acrylates below 0.10 quality %.

The synthetic method of the polymkeric substance of recording in 18. claims 15, wherein, the SP value of above-mentioned solvent (calculating according to rushing Tianjin method) is

mPa ^1/2.

The synthetic method of the polymkeric substance of recording in 19. claims 18, wherein, above-mentioned solvent is ester series solvent.

The synthetic method of the polymkeric substance of recording in 20. claims 19, wherein, above-mentioned solvent is diacetate esters series solvent.

21. compositions, wherein, comprise the polymkeric substance described in any one in claim 1-14, and ketone series solvent or nitrile series solvent.

The composition of recording in 22. claims 21, wherein, the concentration of described polymkeric substance is 2 quality % 50 quality %.

The layered product that 23. compositions that are coated with record in claim 21 on resin base material make.