CN109476799A - The manufacturing method of rubber compounding phenol aldehyde type cocondensation and the cocondensation - Google Patents
The manufacturing method of rubber compounding phenol aldehyde type cocondensation and the cocondensation Download PDFInfo
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- CN109476799A CN109476799A CN201780040760.7A CN201780040760A CN109476799A CN 109476799 A CN109476799 A CN 109476799A CN 201780040760 A CN201780040760 A CN 201780040760A CN 109476799 A CN109476799 A CN 109476799A
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- cocondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
A kind of manufacturing method of phenol aldehyde type cocondensation is provided, the phenol aldehyde type cocondensation, which contains, carrys out phenols one kind or two or more shown in self-drifting (i), the Component units of formaldehyde and resorcinol, Component units from above-mentioned phenols contain the Component units from p-tert-butylphenol of 65 moles of % or more, the manufacturing method successively includes: (1) in the presence of the alkali for being 0.05 mole or more relative to 1 mole of above-mentioned phenols, above-mentioned phenols is set to react the process for obtaining the first rank phenol aldehyde type condensation product of 600 or more the number-average molecular weight in GPC method at 75 DEG C or more with formaldehyde；(2) by the reaction solution containing first rank phenol aldehyde type condensation product obtained in process (1) and the process relative to the acid-mixed conjunction that alkali used in process (1) is equivalent or more；(3) make the process of first rank phenol aldehyde type condensation product with the resorcin reaction relative to 1 mole of 0.5~1.2 mole of above-mentioned phenols.
Description
Technical field
Be used as used in processing technology the present invention relates to rubber bonding agent by alkylphenol or phenylphenol (with
It is otherwise referred to as phenols down) the improvement manufacturing method of obtained phenol aldehyde type cocondensation, the phenolic aldehyde that is obtained by the manufacturing method
Type cocondensation, the resin combination containing the phenol aldehyde type cocondensation and contain the phenol aldehyde type cocondensation or the resin group
Close the rubber composition of object.
Background technique
The rubber enhanced with reinforcing materials such as all-steel cord class, organic fiber classes is needed in tire, banding, hose etc.
In product, the strong bond of rubber and reinforcing material is needed.It is be bonded in order to be carried out with rubber, it is known that with various bonding agents to enhancing
Method that material is handled, the side for cooperating bonding agent together with other various compounding agents in the manufacturing procedure of rubber
Method.In these methods, cooperate the method for bonding agent in spite of having carried out the viscous of reinforcing material in the manufacturing procedure of rubber
Bonding by Vulcanization can be carried out securely by connecing agent processing, therefore be widely adopted.
On the other hand, the bonding agent used in the manufacturing procedure of rubber needs to soften in rubber processing process.As
The implementation temperature of rubber processing process, such as known in the tyre rubber field it is preferable to use the bonding agent is usually 170
DEG C or so (such as Japan rubber association will Vol.73 (2000), No.9, p488-493 (non-patent literature 1)).Therefore, in rubber
For the bonding agent that the manufacturing procedure of glue uses, it is desirable that sufficiently low compared with maximum temperature of its softening point when rubber processing, be
150 DEG C or less.In turn, from the viewpoint of dispersibility when improving using the bonding agent, the bonding agent is preferably reduced as far as possible
Softening point to bonding agent adhesion in preservation degree.As this bonding agent used in the manufacturing procedure of rubber, extensively
Using following cocondensation, the cocondensation is made to the phenols such as tert-octyl phenol or nonylphenol and formalin class
It reacts and obtains condensation product, and made of reacting resorcinol with the condensation product (such as Japanese Unexamined Patent Publication 06-234824 public affairs
It reports (patent document 1)).
But tert-octyl phenol and nonylphenol is had become in the REACH regulation of regulation in the region EU at present and provided
SVHC (pay high attention to substance) candidate substances, be likely to limit its use from now in the region EU.
Therefore, the bonding agent as the manufacturing procedure for rubber is being developed, using except to tert-octyl phenol and to nonyl
Phenols other than base phenol, contain the cocondensation from phenol and the Component units of resorcinol.For example, Japanese Unexamined Patent Publication
A kind of cocondensation and its manufacturing method are described in 2014-152220 bulletin (patent document 2), the cocondensation is only to make
Use p-tert-butylphenol as the cocondensation of phenols, softening point is 80 DEG C or more and 190 DEG C or less.Therefore, the present inventor
Supplementary test has been carried out to the method recorded in the document, know that the hygroscopicity of obtained cocondensation is high, be easy adhesion.
In turn, using obtained cocondensation as the bonding agent for the manufacturing procedure for being used for rubber in use, generating rubber pange etc.
Problem specifies that it is not suitable as the bonding agent.
In addition, Japanese Unexamined Patent Publication 2015-052097 bulletin (patent document 3) describes a kind of cocondensation, use is to uncle
Butylphenol and o-phenyl phenol are formed as phenols.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 06-234824 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-152220 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2015-052097 bulletin
Non-patent literature
Non-patent literature 1: Japan rubber association will Vol.73 (2000), No.9, p488-493
Summary of the invention
Problems to be solved by the invention
Specify in patent document 3: when p-tert-butylphenol is used only as phenols, softening point is (200 DEG C very high
More than), it is not suitable as the bonding agent of the manufacturing procedure for rubber, therefore and make the soft of cocondensation with o-phenyl phenol
Change point to decline to a great extent, the bonding agent that can be suitable as the manufacturing procedure for rubber uses.But o-phenyl phenol is more high
It is expensive, it is expected in possible situation not and with o-phenyl phenol or reduces its usage amount to the greatest extent.
Therefore, can present inventors have studied reduce o-phenyl phenol based on method described in Patent Document 3
Usage amount, as a result, if the usage rate of p-tert-butylphenol is relative to the total of o-phenyl phenol and p-tert-butylphenol
Amount more than 65mol%, then make resorcinol with reacted as phenols and formalin obtained from first rank phenol aldehyde type condensation product it is anti-
At once, the swelling, foaming etc. of reaction solution cause mobility to decline, and the unevenness for generating reaction solution homogenizes, and treatability is significantly deteriorated, because
This has the situation that industrial manufacture becomes difficult, and the softening point for having obtained cocondensation can be more than 150 DEG C
Situation.
The purpose of the present invention is to provide a kind of cocondensation and its manufacturing method, the cocondensation is to tert-butyl
Phenol phenol aldehyde type cocondensation as main component, softening point and conventionally known phenol aldehyde type cocondensation are equal extent, and
And adhesion when saving, bonding agent used in the manufacturing procedure as rubber have sufficient performance.
The means used to solve the problem
The present inventors has made intensive studies to solve technical problem, as a result, it has been found that, by following specific
Under the conditions of manufacture containing the phenol aldehyde type cocondensations of following Component units be able to solve above-mentioned technical problem, wherein the composition
Unit, which comes from, makees phenols, formaldehyde and resorcinol as main component containing p-tert-butylphenol.Specifically, including below
Invention.
〔1〕
A kind of manufacturing method of phenol aldehyde type cocondensation,
Above-mentioned phenol aldehyde type cocondensation contain one kind or two or more phenols shown in the following general formula (i), formaldehyde and
The Component units of resorcinol, the Component units from above-mentioned phenols contain 65 moles of % or more from p-tert-butylphenol
Component units,
[changing 1]
R indicates the alkyl or phenyl that can have the carbon number 1~12 of branch,
Above-mentioned manufacturing method successively contains following processes (1), (2) and (3):
(1) in the presence of the alkali for being 0.05 mole or more relative to 1 mole of above-mentioned phenols, make above-mentioned phenols and formaldehyde 75
DEG C or more react obtain the number-average molecular weight (Mn) in gel permeation chromatography (GPC) method be 600 or more first rank phenol aldehyde type contract
The process for closing object；
(2) by the reaction solution containing first rank phenol aldehyde type condensation product obtained in above-mentioned operation (1) and relative to above-mentioned operation
(1) alkali used in is the process that the acid-mixed of equivalent or more is closed；
(3) make above-mentioned first rank phenol aldehyde type condensation product and the isophthalic two relative to 1 mole of 0.5~1.2 mole of above-mentioned phenols
The process of phenol reaction.
〔2〕
The manufacturing method of the phenol aldehyde type cocondensation according to (1), wherein the usage amount of above-mentioned resorcinol relative to
1 mole of above-mentioned phenols is 0.5~0.8 mole.
〔3〕
According to the manufacturing method of phenol aldehyde type cocondensation described in (1) or (2), wherein alkali used in above-mentioned operation (1)
Usage amount relative to 1 mole of above-mentioned phenols be 0.05~0.25 mole.
〔4〕
A kind of phenol aldehyde type cocondensation, meets the whole in following (a)~(e),
(a) containing the composition list for coming from phenols one kind or two or more shown in the following general formula (i), formaldehyde and resorcinol
Member,
[changing 2]
R indicates the alkyl or phenyl that can have the carbon number 1~12 of branch,
(b) Component units from above-mentioned phenols contain the composition list from p-tert-butylphenol of 65 moles of % or more
Member,
(c) number-average molecular weight (Mn) in gel permeation chromatography (GPC) method is 750 or more,
(d) softening point is 80~150 DEG C,
(e) relative to 1 mole of Component units from above-mentioned phenols, the Component units from resorcinol are 0.80 mole
Below.
〔5〕
The phenol aldehyde type cocondensation according to (4), also meets following (f),
(f) peak top molecular weight in gel permeation chromatography (GPC) method in terms of area percentage containing 1~10% is 700
~520 ingredient (oligomer 1), the ingredient that the peak top molecular weight in terms of area percentage containing 0.01~2% is 430~320
(oligomer 2).
〔6〕
According to phenol aldehyde type cocondensation described in (4) or (5), wherein 2.0g phenol aldehyde type cocondensation is dissolved in 20mL
Spectral transmission of the solution made of tetrahydrofuran at wavelength 610nm is 80% or more.
〔7〕
A kind of resin combination contains phenol aldehyde type cocondensation and softening agent described in any one of (4)~(6).
〔8〕
The resin combination according to (7), wherein above-mentioned softening agent is the fatty acid of carbon number 8~32.
〔9〕
The resin combination according to (7), wherein above-mentioned softening agent is cashew nut shell liquid (CNSL).
〔10〕
The resin combination according to any one of (7)~(9), wherein above-mentioned softening agent in resin combination
Content is 5~40 weight %.
〔11〕
The resin combination according to any one of (7)~(10), wherein 2.0g resin combination is dissolved in 20mL
Spectral transmission of the solution made of tetrahydrofuran at wavelength 610nm is 80% or more.
〔12〕
A kind of rubber composition contains phenol aldehyde type cocondensation described in any one of (4)~(6) or (7)~(11)
Any one of described in resin combination and rubber constituent.
Invention effect
Decline in accordance with the invention it is possible to not generate the mobility as caused by swelling, foaming of reaction solution etc. during fabrication, is anti-
It with p-tert-butylphenol is main to manufacture under conditions of answering the unevenness of liquid the problem of of becoming the obstacle industrially implemented such as to homogenize
When the phenol aldehyde type cocondensation of ingredient, i.e. softening point and conventionally known phenol aldehyde type cocondensation are equal extent and save not
Adhesion, the cocondensation as the bonding agent of the manufacturing procedure for rubber with sufficient performance.
In turn, manufacturing method according to the invention, even by conventionally known method, softening point is high and unsuitable
Bonding agent as the manufacturing procedure for rubber, phenol aldehyde type cocondensation using only p-tert-butylphenol as phenols,
Also the softening point of the cocondensation can be made to be reduced under conditions of not reducing the performance as bonding agent can be as rubber
The degree that the bonding agent of the manufacturing procedure of glue uses.In addition, an embodiment of manufacturing method according to the invention, additionally it is possible to mention
For keeping performance and cocondensation that is as needed and improving foul smell as bonding agent.
To sum up, specify phenol aldehyde type cocondensation that manufacturing method through the invention obtains in addition to cashew nut shell liquid (CNSL)
In addition, and by the fatty acid of the carbon number 8~32 of representative of stearic acid also there is compatibility.Processing of the above-mentioned fatty acid in rubber
Vulcanization aid is commonly used as in process, therefore when wanting to further decrease the softening point of cocondensation of the invention, without making
Use substance rarely needed in the manufacturing procedure of rubber as softening agent, even if in the substance meeting being separately added as softening agent
Cause to properly use in the purposes (such as softening agent with other ingredients react contained in rubber rubber) of problem.
Specific embodiment
The manufacturing method > of < phenol aldehyde type cocondensation
The manufacturing method of phenol aldehyde type cocondensation of the invention is described in detail.Phenol aldehyde type cocondensation of the invention
Manufacturing method be characterized in that, successively containing following (1), (2) and (3) process.
(1) in the alkali for being 0.05 mole or more relative to phenols one kind or two or more shown in 1 mole of above-mentioned general formula (i)
In the presence of, it reacts phenols one kind or two or more shown in above-mentioned general formula (i) at 75 DEG C or more with formaldehyde, obtains gel infiltration
The process for the first rank phenol aldehyde type condensation product that number-average molecular weight (Mn) in chromatography (GPC) method is 600 or more.
(2) reaction solution containing first rank phenol aldehyde type condensation product obtained in process (1) is used with relative in process (1)
Alkali be equivalent more than acid-mixed close process.
(3) make first rank phenol aldehyde type condensation product and relative to phenols one kind or two or more shown in 1 mole of above-mentioned general formula (i)
For the process of 0.5~1.2 mole of resorcin reaction.
It is (following as phenols one kind or two or more shown in above-mentioned general formula (i) when implementing the manufacturing method of the present invention
Otherwise referred to as phenols), the use ratio of p-tert-butylphenol the high, more can more inexpensively manufacture phenol aldehyde type cocondensation of the invention
Object is closed, the phenols other than p-tert-butylphenol also can be used together.As can p-tert-butylphenol other than phenols, can example
Show o-tert-butylphenol, o-phenyl phenol, p-phenyl phenol, paracresol, have and can have to tert-octyl phenol, nonylphenol etc.
There is phenols of the alkyl or phenyl as substituent group that the carbon number of branch is 1~12.In these phenols, from the above-mentioned legal provisions of reply
From the perspective of, it is preferably provided with the phenols for the alkyl or phenyl that can have that the carbon number of branch is 1~6, particularly preferred o-tert-butyl
Phenol, o-phenyl phenol, p-phenyl phenol and paracresol.P-tert-butylphenol when other phenols, in whole phenols
The usage amount of other phenols in addition is usually 35 moles of % hereinafter, price and obtained phenol aldehyde type cocondensation from other phenols
From the perspective of object is closed to the dissolubility of the fatty acid of carbon number 8~32, preferably 20 moles of % are hereinafter, more preferably 10 rub
That % is hereinafter, be particularly preferably set as 5 moles of % or less.
As formaldehyde used in process (1), other than gasiform formaldehyde, also can be used formaldehyde aqueous solution,
I.e. formalin and paraformaldehyde and trioxane etc. can be easy to produce the compound of formaldehyde.As the usage amount of formaldehyde, such as
It is preferably 1~3 mole, more preferably 1.5~2.5 moles relative to 1 mole of phenols.By using 1 mole or more, it is able to suppress
The generation of volatile organic compounds；In addition, by the way that usage amount is set as 3 moles hereinafter, so as to make obtained phenolic aldehyde
The softening point of type cocondensation further decreases.
As alkali used in process (1), can be used alkali and alkaline earth metal ions hydroxide or carbonate, ammonia,
Used alkali when the common manufacture first rank phenol aldehyde type condensation product such as amine.As the specific example of these alkali, hydroxide can be enumerated
Sodium, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate etc..In these alkali, preferably sodium hydroxide, potassium hydroxide.These alkali can
To use a kind or as needed be used in mixed way two or more.In addition, solid or liquid can be used in these alkali, (aqueous solution has
Machine solution), the preferred aqueous solutions from reactivity and the angle that is easily processed.When using aqueous solution, institute in aqueous solution
The alkali contained is usually 10 weight of weight %~50 %.For the usage amount of alkali, need to rub using 0.05 relative to 1 mole of phenols
More than you, preferably 0.05~0.8 mole, more preferably 0.2~0.5 mole.When the usage amount of alkali is less than 0.05 mole, have
Unreacted monomer becomes the case where more, foul smell and volatile organic compounds increase and is difficult to obtain gel permeation chromatography (GPC)
The case where first rank phenol aldehyde type condensation product that number-average molecular weight (Mn) in method is 600 or more.It should be noted that needing to reduce
When the phenol aldehyde type cocondensation of foul smell, preferably the usage amount of alkali is set as 0.05 mole or more, 0.25 relative to 1 mole of phenols
Mole or less.The reasons why being set as 0.25 mole or less then foul smell is reduced the usage amount of alkali is still uncertain, and deduction is due to inhibiting
As caused by the formaldehyde and alkali side reaction product of Cannizzaro reaction, formose reaction etc.
When implementing process (1), organic solvent also can be used.It can be suitable for use example as workable organic solvent
The ketone of the carbon numbers 3~7 such as such as aromatic hydrocarbon, methyl iso-butyl ketone (MIBK) of toluene, dimethylbenzene, ethylo benzene.These organic solvents can
To use a kind or as needed be used in mixed way two or more.For usage amount when using organic solvent, relative to 1 weight
Phenols again is usually 0.4~4.0 times of weight.When being reacted without using organic solvent, water can be used also to replace
Organic solvent.
It is added to as the method for implementing process (1), such as by phenols and formaldehyde, organic solvent used as needed
After in reactor, alkali is further added in reactor to and is made alkali soluble solution or suspension and implements to react.Implementing the reaction
When, it needs suitably to analyze reaction solution with gel permeation chromatography (GPC), implements reaction to standard polystyren conversion molecule
Until the number-average molecular weight (Mn) of first rank phenol aldehyde type condensation product in meter, reaction solution reaches 600 or more.In addition, usually reaction
The number-average molecular weight (Mn) of first rank phenol aldehyde type condensation product in liquid is 1500 or less.If the first rank phenol aldehyde type contracts in process (1)
The number-average molecular weight (Mn) for closing object is lower than 600, then reacts aftermentioned with generation in the process (process (3)) of resorcin reaction
Liquid swelling, mobility decline, reaction solution unevenness homogenize etc as the obstacle industrially implemented the problem of, asked to solve this
Topic, it is intended to the hot conditions or high stirring intensity condition for needing industrially to be difficult to carry out.In addition, being stirred in the hot conditions or height
It mixes after implementing reaction under strength condition, whens reducing moisture, unreacted phenols, solvent etc. from obtained phenol aldehyde type cocondensation
The softening point for being easy to make the cocondensation is more than 150 DEG C, is not suitable for being matched with rubber when being kneaded as institute in this case
The bonding agent of the rubber and reinforcing material that use.It should be noted that after the number-average molecular weight of first rank phenol aldehyde type condensation product passes through
The method recorded in the embodiment stated determines.
In order to implement process (1) and obtain the first rank phenol aldehyde type condensation product that number-average molecular weight (Mn) is 600 or more, usually will
Reaction temperature is set as 75 DEG C or more, preferably 75~120 DEG C.When to implement reaction lower than 75 DEG C, it becomes difficult to be counted
The first rank phenol aldehyde type condensation product that average molecular weight (Mn) is 600 or more.It should be noted that when implementing the reaction of process (1), no
Need to be always 75 DEG C or more, as long as any moment in the reaction reaches 75 DEG C or more.
Process (2) can by by containing first rank phenol aldehyde type condensation product obtained in process (1) reaction solution and be process
(1) the acid-mixed more than equivalent of alkali used in is closed to implement.As acid used in process (2), it can be mentioned, for example: hydrochloric acid,
The inorganic acids such as sulfuric acid, nitric acid, phosphoric acid；The organic acids such as formic acid, acetic acid, oxalic acid, p-methyl benzenesulfonic acid.These acid can be used a kind or
Two or more is used in mixed way, alternatively, it is also possible to use the aqueous solution of these acid.As long as the usage amount of acid is relative in process (1)
The alkali composition of the alkali used is equivalent or more, is 1~2 mole preferably with respect to 1 mole of alkali composition.Process (2) can also be with
Implement in the following manner: the mixing of reaction solution and acid containing first rank phenol aldehyde type condensation product obtained in process (1) is divided into number
Secondary, the total amount of used acid is the equivalent of alkali used in process (1) or more.
There is following situation at not firm construction sequence (2): making obtained phenol aldehyde type cocondensation is made an addition to rubber
Used time deteriorates the physical property of vulcanized rubber etc., cannot give full play to the performance of the bonding agent as the manufacturing procedure for rubber.
And then have following situation: when in process (3) with resorcin reaction, reaction carries out obtaining insufficient and remaining a large amount of unreacted phenol
Class；And when removing unreacted phenols, resorcinol etc., because coloring or obtained phenol aldehyde type cocondensation occur for the alkali of remaining
Object is decomposed, and the quality decline as bonding agent is caused.In addition, can reduce obtained cocondensation by implementing process (2)
Close the hygroscopicity of object.
After implementing process (2), in order to remove the inorganic salts etc. of unreacted formaldehyde and by-product, implementation can according to need
First rank phenol aldehyde type condensation product is extracted into organic by washing step, the washing step using water-immiscible organic solvent and water
Xiang Zhong separates the inorganic salts of unreacted formaldehyde, by-product into water phase.
The usage amount of resorcinol used in process (3), which needs 1 mole relative to phenols used in process (1), to be made
Dosage is 0.5~1.2 mole, preferably 0.5~1.0 mole, more preferably 0.5~0.8 mole.When the usage amount of resorcinol
When more than 1.2 moles, there are problems that the case where a large amount of remainings of unreacted resorcinol, volatility become.In addition, being difficult to
To the tendency of the phenol aldehyde type cocondensation compatible well with stearic acid.When the usage amount of resorcinol is less than 0.5 mole, deposit
The case where not showing the performance as the bonding agent of the manufacturing procedure for rubber and obtained phenol aldehyde type cocondensation
Molecular weight get higher, 150 DEG C or less of situation is not achieved in softening point.
Process (3) can also be implemented without using solvent, preferably relative to 1 times of weight of phenols used in process (1)
To implement in the presence of solvent more than 0.2 times of weight, more preferably implement in the presence of the solvent of 0.4~2.0 times of weight.By making
With solvent more than 0.2 times of weight, it can be avoided the producing high-molecular of obtained phenol aldehyde type cocondensation and can reduce institute
Unreacted resorcinol content in obtained phenol aldehyde type cocondensation.In addition, by the way that the usage amount of solvent is set as 2.0 weights
Amount times hereinafter, it is desirable that from cocondensation except solvent used in dereaction in the case where, can efficiently by the solvent from
It is removed in cocondensation.As workable solvent in process (3), it can be mentioned, for example: the fragrance such as toluene, dimethylbenzene, ethylo benzene
Race's hydrocarbon；The ketone of the carbon numbers such as methyl iso-butyl ketone (MIBK) 3~7；With ethyl acetate, n-propyl acetate, isopropyl acetate, the positive fourth of acetic acid
Ester, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, methyl amyl acetate, acetic acid 2- ethyl butyl ester, fourth
The esters such as acetoacetic ester, methyl valerate system organic solvent, preferably toluene, dimethylbenzene, n-butyl acetate.Solvent used in process (3)
Both it can be directly used in solvent used in the washing step suitably implemented after process (1) and/or process (2), it can also
New solvent is suitably added.
The reaction of process (3) is usually implemented at 40~150 DEG C, preferably 100~150 DEG C.In addition, being condensed in first rank phenol aldehyde type
In the reacting of object and resorcinol, if there are water in system, reaction speed can be made slack-off, therefore preferably on one side will be secondary in reaction
The water of production is removed to implementation reaction on one side outside system.
The available phenol aldehyde type cocondensation of the invention with aftermentioned feature after process (3) terminates is needing
Will solvent, unreacted phenols, resorcinol etc. used in reaction contained in the phenol aldehyde type cocondensation when removing, can be with
Removing is concentrated using conventional method (to be sometimes also known as this process removal step is concentrated below.).It should be noted that in reality
When applying concentration removal step, Ruo Neiwen is more than that 165 DEG C of softening points that then there is obtained phenol aldehyde type cocondensation are easy to reach
150 DEG C or more, become difficult to the case where using as the bonding agent of the manufacturing procedure for rubber and phenol aldehyde type cocondensation
Situations such as coloring, decomposition.
Phenol aldehyde type cocondensation > < of the invention
Phenol aldehyde type cocondensation of the invention has the feature of following (a) and (b).
(a) containing the composition list for coming from phenols one kind or two or more shown in above-mentioned general formula (i), formaldehyde and resorcinol
Member.
(b) Component units from above-mentioned phenols contain the composition list from p-tert-butylphenol of 65 moles of % or more
Member.Component units from above-mentioned phenols contain preferably 80 moles of % or more, more preferable 90 moles of % or more to tertiary fourth
The Component units of base phenol.
In addition, phenol aldehyde type cocondensation of the invention usually contains relative to 1 mole of the total amount of the Component units from phenols
There are 1~2 times mole of the Component units (methylene and/or dimethylene ether) from formaldehyde.The ratio of these Component units
It can be used for example1H-NMR analyzes phenol aldehyde type cocondensation to confirming.Specifically, following methods can be illustrated: will be made
The phenol aldehyde type cocondensation made is washed with water equal solvent and removes contained unreacted isophthalic two from phenol aldehyde type cocondensation
The unreacted monomers such as phenol, then utilize1H-NMR is analyzed, by obtained analysis result from each Component units
Proton integration value determines its ratio.
In turn, phenol aldehyde type cocondensation of the invention has the feature of (c) below, (d) and (e).
(c) number-average molecular weight (Mn) in gel permeation chromatography (GPC) method is 750 or more.
(d) softening point is 80~150 DEG C.
(e) 1 mole of Component units relative to one kind or two or more phenols shown in the above-mentioned general formula (i), comes from
The Component units of resorcinol are 0.80 mole or less.
Number-average molecular weight (Mn) in gel permeation chromatography (GPC) method of phenol aldehyde type cocondensation of the invention is poly- with standard
Styrene conversion Molecular weights are 750 or more, preferably 1000 or more.When number-average molecular weight is lower than 750, can be generated in preservation
Adhesion.The number-average molecular weight of phenol aldehyde type cocondensation is determined by the method recorded in aftermentioned embodiment.In addition, number is divided equally
Son amount preferably 3000 or less, more preferably 2000 or less.By the way that number-average molecular weight is set as 3000 hereinafter, can make phenol aldehyde type
The softening point of cocondensation further decreases.
The softening point of phenol aldehyde type cocondensation of the invention is 80 DEG C or more, preferably 90 DEG C or more；Furthermore for 150 DEG C with
Under, preferably 140 DEG C or less.When softening point be higher than 150 DEG C when, have the bonding agent in the manufacturing procedure as rubber when using
Disperse the tendency that insufficient, adhesive property plays insufficient in rubber.In addition, holding in preservation when softening point is lower than 80 DEG C
It is also easy to produce adhesion.It should be noted that even if mixed by aftermentioned method with softening agent resin combination is made after conduct
Bonding agent in the manufacturing procedure of rubber is in use, the softening point of phenol aldehyde type cocondensation of the invention is preferably also above-mentioned model
It encloses.
Phenol aldehyde type cocondensation of the invention contains 0.80 mole relative to 1 mole of total amount of the Component units from phenols
Below, preferably 0.30~0.80 mole, more preferable 0.30~0.70 mole of the Component units from resorcinol.Between coming from
When the Component units of benzenediol are more than 0.80 mole, hygroscopicity is got higher, and is sticked together when being easy to produce the holding cocondensation
Problem, when the cocondensation is used as the bonding agent for the manufacturing procedure for being used for rubber the problems such as rubber pange.In addition, working as
There is thixotropy when Component units from resorcinol are more than 0.80 mole, when melting cocondensation due to existing or become
The case where high viscosity liquid and the processing and formings such as poor fluidity, granulating, flaking become difficult and the rouge with carbon number 8~32
The incompatible situation of fat acids.In addition, there is the case where not being embodied as the performance of bonding agent when being less than 0.30 mole.
The ratio of Component units from resorcinol can be determined by the method recorded in aftermentioned embodiment.
In addition, the fatty acid when phenol aldehyde type cocondensation of the invention has feature (f) below, with carbon number 8~32
The compatibility of class improves.
(f) peak top molecular weight in gel permeation chromatography (GPC) method in terms of area percentage containing 1~10% is 700
~520 ingredient (oligomer 1), the ingredient that the peak top molecular weight in terms of area percentage containing 0.01~2% is 430~320
(oligomer 2).
Whether it is as characterized above can be true and being analyzed according to aftermentioned condition with gel permeation chromatography (GPC)
Recognize.
In turn, when it is brown that phenol aldehyde type cocondensation of the invention is uncolored, the cocondensation of foul smell reduction is easily become
Object.Specifically, when cocondensation 2.0g of the invention is dissolved in solution made of tetrahydrofuran 20mL at wavelength 610nm
Spectral transmission be 80% or more when, easily become the cocondensation of foul smell reduction.Spectral transmission at wavelength 610nm
It is determined by the method recorded in aftermentioned embodiment.Coloring and the relationship of foul smell are still not clear, but from colored parts ingredient
Influence whether that the angle of foul smell is set out, thus it is speculated that there are correlativities with foul smell for coloring.
The content of unreacted resorcinol contained in phenol aldehyde type cocondensation of the invention is preferably 8 weight % or less.
By be set as 8 weight % hereinafter, by the bonding agent in manufacturing procedure of the phenol aldehyde type cocondensation directly as rubber in use,
Resorcinol evaporates when being able to suppress compounding rubber, is preferred in operating environment.By phenol aldehyde type cocondensation and softening
Agent mixing and in the form of resin combination in use, unreacted resorcinol content although also depend on phenol aldehyde type cocondensation and
The mixing ratio of softening agent but it is preferably set to 10 weight % or less.In addition, not anti-contained in phenol aldehyde type cocondensation of the invention
The content for answering phenols (one kind or two or more phenols shown in the above-mentioned general formula (i) used as raw material) is preferably 3 weight %
Below, it is more preferably 1 weight % or less.By the content of unreacted phenols is set as 3 weight % hereinafter, can reduce to people and
The adverse effect of the ecosystem.In addition, volatile organic compounds contained in phenol aldehyde type cocondensation of the invention is (according to need
The solvent etc. wanted and used during fabrication) content from environmental preferably 5 weight % or less, more preferably 3 weights
Measure % or less.It should be noted that above-mentioned volatile organic compounds is free of above-mentioned unreacted resorcinol and unreacted phenols.
< resin combination >
Then, the resin combination containing phenol aldehyde type cocondensation and softening agent of the invention is illustrated.(have below
When also will be referred to as resin combination containing the resin combination of phenol aldehyde type cocondensation and softening agent of the invention.)
Softening agent used in the present invention, as long as it is compatible with phenol aldehyde type cocondensation of the invention, can reduce
The substance of the softening point of obtained resin combination.As such substance, can illustrate for example: usually as phenol aldehyde type
The liquid such as solid, the cashew nut shell liquid (CNSL) of the low softening points such as the coumarone resin that the softening agent of cocondensation uses.In turn, lead to
Cross phenol aldehyde type cocondensation and rubber that the manufacturing method of the present invention obtains manufacturing procedure be commonly used as vulcanization aid, with hard
Resin acid is that the fatty acid of the carbon number 8~32 of representative also has compatibility, therefore the fatty acid of carbon number 8~32 can also be used to make
For softening agent.It should be noted that being not based on the manufacturing method of the present invention but being obtained by conventionally known manufacturing method
Phenol aldehyde type cocondensation and carbon number 8~32 fatty acid be it is incompatible, the separation of resin layer and oil reservoir can be generated.
These softening agents, which can be used a kind and also can according to need, is used in mixed way two or more.Especially with carbon number 8
The resin combination of~32 fatty acid, especially stearic acid as softening agent, even if due to the processing for not adding rubber newly
The substance being often used without in process can also reduce its softening point as softening agent, therefore even if as softening agent and separately
The substance of addition will lead in the purposes (such as softening agent can be with other ingredients react contained in rubber rubber) of problem,
It can properly use.
Cashew nut shell liquid is the natural plant liquid obtained by the shell of cashew nut.Cashew nut shell liquid is by with saturated or unsaturated hydrocarbon
The mixture that the amphyl of side chain is constituted.In particular, as its ingredient, mainly contain anacardic acid, anacardol, cardol (
Referred to as cashew nut diphenol), methyl cardol (also referred to as methyl cashew nut diphenol).As the preparation method of cashew nut shell liquid, have heating and
Solvent extraction method, usual industrial cashew nut shell liquid are prepared by heat treatment.By the heat treatment, decarburization occurs for anacardic acid
Acid and be converted to anacardol, therefore anacardol and cardol, methyl cardol are main component, the work that thus usually can be obtained
The composition ratio (weight %) of industry cashew nut shell liquid is anacardol (75~85%), cardol (15~20%), methyl cardol
(1~5%).It should be noted that the cashew nut shell liquid in the present invention refers to: to this and being isolated and purified to cashew nut shell liquid
Each ingredient contained in liquid has carried out the liquid of appropriate adjustment；And other ingredients are not added into cashew nut shell liquid and make it
The cashew nut shell polymeric that a part is polymerized.
As the cashew nut shell liquid that can industrially obtain, it can be mentioned, for example northeast Chemical Co., Ltd cashew nut flowing products
(CNSL, LB-7000, LB-7250, CD-5L), TAN HOA HOP PHAT Co., Ltd corporation CNSL etc..These cashew nut shells
Liquid can be used alone, and also can according to need and is used in mixed way two or more.
The fatty acid for being 8~32 as carbon number, it can be mentioned, for example the saturated or undersaturated aliphatic acid of carbon number 8~32 or
Their metal salt.Specifically, can be enumerated as saturated fatty acid: octanoic acid (octanoic acid), n-nonanoic acid, capric acid, ten
One carbonic acid, lauric acid, myristic acid, palmitinic acid, stearic acid and behenic acid etc.；As unsaturated fatty acid, can enumerate: oleic acid
Or undecenoic acid etc..These fatty acids can be used a kind or be two kinds or more as needed.In these fatty acids,
From the viewpoint of price, be easy to start with, preferably stearic acid, palmitinic acid, myristic acid, lauric acid and behenic acid.In addition, hard
Resin acid be as the additive in rubber and common are machine acid, therefore particularly preferably.
Stearic specific example used in the present invention, it can be mentioned, for example Japan Oil Co's bead stearic acid
Camellia (C18:63%, C16:32%), bead stearic acid oriental cherry (C18:66%, C16:31%) etc..
The content of softening agent contained in resin combination is 5 weight % or more, excellent relative to the total amount of resin combination
10 weight % or more are selected as, are in addition 40 weight % or less, preferably 30 weight % or less.By the way that content is set as 40 weight %
Hereinafter, the adhesion of resin combination and the reduced performance as rubber bonding agent can be reduced；By the way that content is set as 5 weights
% or more is measured, softening point reducing effect can be given full play to.
When being kneaded resin combination of the invention in conventional melting temperature i.e. 170 DEG C or so into rubber, the resin
The softening point of composition be 150 DEG C or less be sufficiently, but in order to inhibit resorcinol to evaporate in mixing and 100~130
When being kneaded in a low temperature of DEG C, if softening point is not set below melting temperature i.e. 120 DEG C hereinafter, if exist generate point
, there is the case where performance for being unable to give full play the bonding agent as rubber and reinforcing material in the case where dissipating property bad problem.
In addition, can stick together in preservation sometimes when the softening point of resin combination is lower than 80 DEG C, therefore not preferably.
It is brown when resin combination of the invention is uncolored in the same manner as the phenol aldehyde type cocondensation of aforementioned present invention
When, easily become the resin combination of foul smell reduction.Specifically, when 2.0g resin combination of the invention is dissolved in 20mL
When spectral transmission of the solution made of tetrahydrofuran at wavelength 610nm is 80% or more, the tree of foul smell reduction is easily become
Oil/fat composition.Spectral transmission at wavelength 610nm can be determined by the method recorded in aftermentioned embodiment.
The content of unreacted resorcinol contained in resin combination is preferably 8 weight % or less.By being set as 8 weights
% is measured hereinafter, being able to suppress resorcinol evaporation in compounding rubber, is preferred in operating environment.In addition, resin combination
The content of unreacted phenols contained in object is preferably 3 weight % or less, more preferably 1 weight % or less.By by unreacted
The content of phenols is set as 3 weight % hereinafter, so as to reduce the adverse effect to people and the ecosystem.In addition, resin combination
The content of volatile organic compounds contained in object (solvent etc. used as needed and during fabrication) goes out in terms of environment
It sends out and preferably 5 weight % or less, more preferably 3 weight % or less.It should be noted that above-mentioned volatile organic compounds is not
Containing above-mentioned unreacted resorcinol and unreacted phenols.
Above-mentioned resin combination can be of the invention by obtaining the method for utilizing above-mentioned operation (1), (2) and (3)
Phenol aldehyde type cocondensation and softening agent mixing are to obtain.It, can be according to need after mixing softening agent or before mixing softening agent
Implement the concentration removal step except solvent, unreacted p-tert-butylphenol, resorcinol used in dereaction etc..
When the softening agent contained in the resin combination is the fatty acid of carbon number 8~32, by making first rank phenol aldehyde type
Condensation product and (process (3)) when resorcin reaction make this react the saturated or undersaturated aliphatic acid presence in carbon number 8~32
Lower implementation, so as to manufacture resin combination of the invention.By making process (3) in the saturation or unsaturation of carbon number 8~32
Fatty acid in the presence of implement, so as to be readily derived, remaining resorcinol amount is few and softening point is 80~120 DEG C, i.e. ratio
Lower resin combination.When in process (3) using the saturated or undersaturated aliphatic acid of carbon number 8~32, usage amount is opposite
100 parts by weight of total amount of Yu Jiajie phenol aldehyde type condensation product and resorcinol are usually 15~40 parts by weight, preferably 15~35
Parts by weight, more preferably 18~32 parts by weight.
< rubber composition >
Then, the rubber composition containing phenol aldehyde type cocondensation and/or resin combination of the invention is carried out detailed
Explanation.
Rubber composition of the invention contains above-mentioned phenol aldehyde type cocondensation and/or resin combination and rubber constituent, allusion quotation
It, can be by phenol aldehyde type cocondensation and/or resin combination, rubber constituent, filler, sulphur and methylene donor in the case of type
Object mixing is closed to obtain.Vulcanization accelerator, zinc oxide, organic cobalt compounds can also be kneaded together with above-mentioned each ingredient.
Phenol aldehyde type cocondensation of the invention and/or resin combination for example with every 100 parts by weight of rubber ingredient be 0.5~
The range of 10 parts by weight come using.Wherein, the preferred range of 1~5 parts by weight.When less than 0.5 parts by weight, it can not be effective as
The bonding agent of reinforcing material and rubber plays a role；When more than 10 parts by weight, although there is no problem in terms of above-mentioned effect, nothing
Method embodies the effect being consistent with additive amount, economically not preferably.
As rubber constituent, in addition to natural rubber, epoxy natural rubber, deproteinized natural rubber and other modified naturals
Other than rubber, polyisoprene rubber (IR), styrene butadiene copolymers rubber (SBR), polybutadiene rubber can be also illustrated
(BR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene-isobutene copolymer rubber (IIR), ethylene/propylene/diene
The various synthetic rubber such as copolymer rubber (EPDM), halogenated butyl rubber (HR) are, it is preferable to use natural rubber, styrene-butadiene
The high unsaturation rubber such as copolymer rubber, polybutadiene rubber.Particularly preferred natural rubber.In addition, natural rubber and styrene-
It is butadiene copolymer rubber and with, natural rubber and polybutadiene rubber and with etc. the combinations of a variety of rubber constituents be also effective
's.
As the example of natural rubber, the natural rubber of the grades such as RSS#1, RSS#3, TSR20, SIR20 can be enumerated.As
Epoxy natural rubber, preferably epoxidation degree are the rubber of 10~60 moles of %, can illustrate such as Kumplan Guthrie
Berhad corporation ENR25, ENR50.As deproteinized natural rubber, preferably total nitrogen content percentage is 0.3 weight % below de-
Protein natural rubber.As modified natural rubber, it is preferable to use making 4-vinylpridine, acrylic acid N, N- dialkyl amido in advance
Ethyl ester (such as acrylic acid N, N- diethylamino ethyl ester), 2- hydroxy acrylate etc. contain pole obtained by reacting with natural rubber
The modified natural rubber of property group.
As the example of SBR, Japan rubber association can be enumerated and compile " rubber industry brief guide (go system industry Bian list) < fourth edition
The emulsion polymerization SBR and polymerisation in solution SBR of > " page 210~211 record.Polymerisation in solution SBR is particularly preferably used, more preferably
It uses:
4,4 '-bis- (dialkyl amido) benzophenone pair such as Japanese ZEON corporation " Nipol (registered trademark) NS116 "
Polymerisation in solution SBR that molecular end is modified,
Polymerisation in solution SBR that JSR corporation " SL574 " etc. is modified molecular end with halogenation tin compound,
The commercially available product of the silane-modified polymerisation in solution SBR such as Asahi Kasei Corporation's system " E10 ", " E15 ",
Exclusive use lactam compound, amide compound, urea based compound, N, N- dialkylacrylamides compound,
Isocyanate compound, imide compound, silane compound (trialkoxy silane compound etc.), amino with alkoxy
Any pair of molecular end in silane compound in molecular end has nitrogen, tin, any in silicon obtained from being modified
The polymerisation in solution SBR of kind element,
Using be selected from lactam compound, amide compound, urea based compound, N, N- dialkylacrylamides compound,
Isocyanate compound, imide compound, silane compound (trialkoxy silane compound etc.) and ammonia with alkoxy
Two or more compound (tin compound and silane compound with alkoxy, alkyl acryl amination in base silane compound
Close object and the silane compound etc. with alkoxy) molecular end is modified obtained from molecular end with being selected from
The polymerisation in solution SBR of two or more element in nitrogen, tin and silicon.
As the example of BR, can illustrate the high-cis BR, cis- key that cis- Isosorbide-5-Nitrae key is 90% or more be 35% or so it is low
The polymerisation in solutions such as cis- BR BR, it is preferable to use high-vinyl-content low cis BR.More preferably use:
The tin modifications BR such as Japanese ZEON system " Nipol (registered trademark) BR 1250H ",
4,4 '-bis- (dialkyl amido) benzophenone, halogenation tin compound, lactam compound, amidation are used alone
Object, urea based compound, N are closed, N- dialkylacrylamides compound, imide compound, has alcoxyl at isocyanate compound
Any pair of molecular end in the silane compound (trialkoxy silane compound etc.) of base, amino silane compounds changes
Property obtained from molecular end have nitrogen, tin, any element in silicon polymerisation in solution BR,
Using selected from 4,4 '-bis- (dialkyl amido) benzophenone, halogenation tin compound, lactam compound, amidation
Object, urea based compound, N are closed, N- dialkylacrylamides compound, imide compound, has alcoxyl at isocyanate compound
Two or more compound (tin chemical combination in the silane compound (trialkoxy silane compound etc.) and amino silane compounds of base
Object with alkoxy silane compound, alkyl acryl amine compounds with the silane compound etc. of alkoxy) to dividing
Sub- end in molecular end has the polymerisation in solution BR of two or more element in nitrogen, tin and silicon obtained from being modified.
These BR are usually used with natural rubber compound.
Rubber constituent preferably comprises natural rubber, and natural rubber ratio shared in rubber constituent is preferably 70 weight %
More than.
As filler, carbon black usually used in rubber materials, silica, talcum, clay, hydroxide can be illustrated
Aluminium, titanium oxide etc. are, it is preferable to use carbon black and silica particularly preferably use carbon black in turn.As carbon black, it can be mentioned, for example
Carbon black of " rubber industry brief guide < fourth edition > " page 494 record is compiled by Japan rubber association, preferably, HAF (High
Abrasion Furnace)、SAF(Super Abrasion Furnace)、ISAF(Intermediate SAF)、FEF(Fast
Extrusion Furnace)、MAF(Medium Abrasion Furnace)、GPF(General Purpose Furnace)、
The carbon blacks such as SRF (Semi-Reinforcing Furnace).As rubber composition for tire tread, it is preferable to use ctab surface product
For 40~250m2/ g, N2 adsorption specific surface area are 20~200m2/ g, the carbon black that partial size is 10~50nm, further preferred CTAB
Surface area is 70~180m2The carbon black of/g, as its example, can enumerate N110, N220 in ASTM standard, N234, N299,
N326, N330, N330T, N339, N343, N351 etc..In addition, it is also preferred that the surface of carbon black is attached with the two of 0.1~50 weight %
The surface-treated carbon black of silica.In turn, carbon black and silica and with etc. by the mode that a variety of fillers combine be also to have
Effect.
As silica, can illustrate CTAB specific surface area is 50~180m2/ g, N2 adsorption specific surface area be 50~
300m2The silica of/g is, it is preferable to use Tosoh silication work Co. Ltd. system " AQ ", " AQ-N ", goldschmidt chemical corporation system
" ULTRASIL (registered trademark) VN3 ", " ULTRASIL (registered trademark) 360 ", " ULTRASIL (registered trademark) 7000 ", Luo Di
Sub- corporation " ZEOSIL (registered trademark) 115GR ", " ZEOSIL (registered trademark) 1115MP ", " ZEOSIL (registered trademark)
1205MP ", " ZEOSIL (registered trademark) Z85MP ", Japanese silica company (Japanese シ リ カ society) make " NIPSEAL (registration
Trade mark) commercially available products such as AQ ".In addition, preferably addition is selected from bis- (tri- ethoxies of 3- usually when using silica as filler
Base silylpropyl) tetrasulfide (goldschmidt chemical corporation system " Si-69 "), bis- (3- triethoxysilylpropyltetrasulfide) curing
Object (goldschmidt chemical corporation system " Si-75 "), bis- (3- diethoxymethyl silylpropyl) tetrasulfides, bis- (3- diethoxies
Methyl silicane base propyl) disulphide and thio-octanoic acid S- [3- (triethoxysilyl) propyl] ester (General
Electric SiliconInc. system " NXT シ ラ Application ") one or more of silane coupling agent etc., have can be with silica
The compound of the functional groups such as the elements such as the silicon of bonding or alkoxy silane.
As aluminium hydroxide, can illustrate N2 adsorption specific surface area is 5~250m2/ g, DOP is 50~100ml/ to oil mass
The aluminium hydroxide of 100g.
The usage amount of the filler is not particularly limited, and preferably every 100 parts by weight of rubber ingredient is 10~120 parts by weight
Range.Particularly preferably 30~70 parts by weight.
Filler preferably comprises carbon black, and carbon black ratio shared in filler is preferably 70 weight % or more.
As sulphur ingredient, powder sulphur, sedimentation sulphur, colloid sulphur, insoluble sulfur and polymolecularity sulphur etc. can be enumerated.Generally preferably
For powder sulphur, when structural tire part more than the sulfur contents such as the banding component for tire, preferred insoluble sulfur.The usage amount of sulphur ingredient
It is not particularly limited, preferably every 100 parts by weight of rubber ingredient is the range of 1~10 parts by weight.In banding component of tire etc.
The preferably range of 5~10 parts by weight.
As the example of vulcanization accelerator, rubber industry handbook < fourth edition > (Heisei corporations' on January 20th, 6 can be enumerated
Legal person, the distribution of Japan rubber association) the thiazole system vulcanization accelerator recorded of page 412~413, the vulcanization of sulfenamide system promote
Agent, guanidine system vulcanization accelerator.
Specifically, it can be mentioned, for example N cyclohexyl 2 benzothiazole sulfenamides (CBS), N- tert-butyl -2- benzo thiophene
Azoles sulfenamide (BBS), N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), two
Benzothiazole disulphide (MBTS), diphenylguanidine (DPG).Wherein, preferred N cyclohexyl 2 benzothiazole sulfenamide
(CBS), N tert butyl benzothiazole 2 sulfenamide (BBS), N, N- dicyclohexyl -2-[4-morpholinodithio sulfenamide (DCBS)
Or bisbenzothiazole disulphide (MBTS) and diphenylguanidine (DPG) are used in combination.
The usage amount of vulcanization accelerator is not particularly limited, and preferably every 100 parts by weight of rubber ingredient is 0.5~3 parts by weight
Range.Wherein, the range of more preferable 0.5~1.2 parts by weight.
The usage amount of zinc oxide is not particularly limited, and preferably every 100 parts by weight of rubber ingredient is the model of 3~15 parts by weight
It encloses.Wherein, the range of more preferable 5~10 parts by weight.
As methylene donor compound, hexa, six (methoxy) melamines, five (first can be enumerated
Oxygroup methyl) it is usually used in the rubber industries such as melamine methylol, four (methoxy) dihydroxymethyl melamines
Methylene donor compound.Wherein, preferably individual six (methoxy) melamine or with its mixing as main component
Object.These methylene donor compounds can use individually or combine two or more and use, relative in 100 parts by weight
Rubber constituent is stated, use level is preferably the range of 0.5~4 parts by weight or so, more preferably the range of 1~3 parts by weight or so.
As organic cobalt compounds, it can be mentioned, for example the cobalt salts of the acid such as cobalt naphthenate, cobaltous octadecanate, fatty acid cobalt-boron network
Polymerisable compounds (such as trade name " MANOBONDO C (registered trademark) ": Rhodia's system) etc..About organic cobalt compounds
Usage amount, relative to the above-mentioned rubber constituent of 100 parts by weight, in terms of cobalt content be preferably 0.05~0.4 parts by weight range.
Rubber composition of the invention can also cooperate the various compounding agents used in rubber materials in the past and be mixed
Refining.As the compounding agent, it can be mentioned, for example anti-aging agent, oil, antiscorching agent, peptizer, stearic acid etc..
As anti-aging agent, it can be mentioned, for example Japan rubber associations to compile " rubber industry brief guide < fourth edition > " the 436th~443
The anti-aging agent that page is recorded.Wherein, it is preferable to use N- phenyl-N ' -1,3- dimethylbutyl-p-phenylenediamine (6PPD), aniline and third
The reaction product (TMDQ) of ketone, poly- (2,2,4- trimethyl -1,2-) dihydroquinoline) (industry companies, Songyuan City system
" Antioxidant FR "), synthetic wax (paraffin etc.), vegetalitas wax.
As oil, technical oil, vegetable fat etc. can be enumerated.As technical oil, paraffin series technical oil, cycloalkanes hydrocarbon system can be enumerated
Technical oil, aromatic system technical oil etc..
As antiscorching agent, phthalic anhydride, benzoic acid, salicylic acid, N- nitrosodiphenylamine int he, N- (hexamethylene can be illustrated
Base is thio)-phthalimide (CTP), sulfamide derivative, diphenyl urea, bis--two phosphorous of (tridecyl) pentaerythrite
Acid esters etc. is, it is preferable to use N- (cyclohexyl thio)-phthalimide (CTP).
Rubber composition containing phenol aldehyde type cocondensation and/or resin combination of the invention for example can be by following
Method obtain.
(A) process that filler and rubber constituent are kneaded
The closed kneading device such as Banbury can be used to carry out in the mixing of filler and rubber constituent.It is described
It is kneaded usually with heat release.Being kneaded temperature when terminating is preferably 140 DEG C~180 DEG C of range, and more preferably 150 DEG C~170
DEG C range.Mixing time is 5 minutes~10 minutes or so.
(B) process that mixture obtained in (A) process, sulphur ingredient and vulcanization accelerator are kneaded
(A) Banbury mixing can be used for example in the mixing of mixture obtained in process, sulphur ingredient and vulcanization accelerator
The closed kneading device such as machine, open roll carry out.The temperature for being kneaded mixture when terminating is preferably 30 DEG C~100 DEG C, more excellent
It is selected as 60 DEG C~90 DEG C.Mixing time is usually 5~10 minutes or so.
The softening point of phenol aldehyde type cocondensation and/or resin combination of the invention is low, thus can in (A) process or
(B) it is added in process, is preferably added in (A) process.
When using zinc oxide, anti-aging agent, oil, fatty acid, peptizer, these are preferably added in (A) process.Make
When with antiscorching agent, preferably it is added in (B) process.
Rubber composition containing obtained phenol aldehyde type cocondensation and/or resin combination of the invention is especially
In the bonding by Vulcanization with reinforcing material effectively.As the reinforcing material, can illustrate nylon, artificial silk, polyester, aramid fiber etc. has
The all-steel cords classes such as machine fiber-like, the all-steel cord for being coated with brass, the all-steel cord for being coated with zinc.Wherein, rubber group of the invention
Close object in the bonding by Vulcanization for the all-steel cord for being coated with brass especially effectively.
By the rubber composition containing phenol aldehyde type cocondensation and/or resin combination of the invention together with reinforcing material
It formed, undergo vulcanization process, so as to obtain the rubber product of rubber Yu reinforcing material strong bond.Vulcanization process is excellent
Choosing is carried out with 120 DEG C~180 DEG C.Vulcanization process carries out under normal pressure or pressurization.
Embodiment
Come more specifically below by way of embodiment, comparative example and reference example (otherwise referred to as embodiment etc. below) is shown
The bright present invention.The present invention is not by any restriction of these examples.It should be noted that about each ingredient recorded in embodiment etc.
Content, residual solvent amount and unreacted monomer amount are then the substance as long as no special declaration relative to containing obtained total
The weight % of the resin combination total amount of condensation product or softening agent, in addition, the content of oligomer ingredient is area percentage.Separately
Outside, the various measurements in each embodiment etc. are implemented according to following.
(1) gel permeation chromatography (GPC) analysis condition
Use equipment: HLC-8220GPC (TOSOH Co., Ltd's system)
Detector: RI (differential refraction) detector
Column: TSK guard column SUPER HZ-L (TOSOH Co., Ltd's system)
+TSK-GEL SUPER HZ1000
+TSK-GEL SUPER HZ2500
+TSK-GEL SUPER HZ4000
Column temperature: 40 DEG C
Injection rate: 10 μ L
Carrier and flow velocity: tetrahydrofuran 0.35mL/ minutes
Find out the standard substance (production of GPC standard curve) of conversion molecular weight: to TSK-GEL standard polystyren reagent
1,1-bis(4-hydroxyphenyl)-cyclohexane (FW268) and phenol (FW94) is added in box (PS- oligomer kit) and makes mark
Directrix curve.
Sample preparation: the cocondensation of about 0.02g or resin combination, reaction mixture are dissolved in tetrahydrofuran
10mL。
Based on by above-mentioned gpc analysis obtain as a result, according to it is following calculate first rank phenol aldehyde type condensation products mean molecules
Institute in the average molecular weight and phenol aldehyde type cocondensation and resin combination of amount, phenol aldehyde type cocondensation and resin combination
The content (area percentage) of each oligomer ingredient contained.
(a) weight average molecular weight (Mw) and number-average molecular weight (Mn) of first rank phenol aldehyde type condensation product
As obtained from the measurement of first rank phenol aldehyde type condensation product multiplet is handled as a whole, and calculates weight
Average molecular weight (Mw) and number-average molecular weight (Mn).It should be noted that in the average molecular weight for calculating first rank phenol aldehyde type condensation product
When, it excludes to be equivalent to the peak of organic solvent and calculate if having used organic solvent when manufacture.
(b) weight average molecular weight (Mw) and number-average molecular weight (Mn) of phenol aldehyde type cocondensation
As obtained from the measurement of phenol aldehyde type cocondensation multiplet is handled as a whole, and it is equal to calculate weight
Molecular weight (Mw) and number-average molecular weight (Mn).It should be noted that when calculating the average molecular weight of phenol aldehyde type cocondensation, row
It is equivalent in the case where having used organic solvent except the peak from unreacted monomer (phenols, resorcinol) and when manufacturing organic
The peak of solvent and calculate.
(c) weight average molecular weight (Mw) and number-average molecular weight (Mn) of resin combination
Multiplet obtained from measurement as resin combination is handled as a whole, and calculates Weight-average molecular
Measure (Mw) and number-average molecular weight (Mn).It should be noted that when calculating the average molecular weight of resin combination, if when manufacture
Organic solvent has been used then to exclude to be equivalent to the peak of organic solvent and calculate.
(d) content of oligomer ingredient
When from the average molecular weight of measurement phenol aldehyde type cocondensation in obtained GPC figure, divide according to the peak valley at each peak
From multiplet, the area percentage of peak top molecular weight (being known as summit in embodiment etc. sometimes below) and the peak at each peak is calculated
(%).It should be noted that when calculating content (area percentage) of oligomer ingredient, if used when manufacture organic molten
Agent then excludes to be equivalent to the peak of organic solvent and calculate.
(2) measurement of unreacted monomer and content of volatile organic compound
For unreacted monomer and content of volatile organic compound, determined based on condition below by gas chromatograph
Amount.
Use equipment: Shimadzu Seisakusho Ltd. corporation gas chromatograph GC-2014
Column: glass column outer diameter 5mm × internal diameter 3.2mm × length 3.1m
Filler: filler Silicone OV-17 10%Chromosorb WHP 80/100mesh, max.temp.340 DEG C
Column temperature: 80 DEG C → 280 DEG C
Gasify room temperature: 250 DEG C
Detector temperature: 280 DEG C
Detector: FID
Carrier gas: N2(40ml/ minutes)
Burning gases: hydrogen (60kPa), air (60kPa)
Injection rate: 2 μ L
Sample preparation condition: the first rank phenol aldehyde type condensation product of 2.0g, phenol aldehyde type cocondensation or resin combination are dissolved
In 10mL titer (acetone soln (about 1g/200mL) of methyl phenyl ethers anisole)
In addition, being 0.1% phenol aldehyde type cocondensation below for unreacted monomer and content of volatile organic compound
Or resin combination, by 2.0g sample be dissolved in 10mL methyl phenyl ethers anisole acetone soln (about 1g/200mL) and according to above-mentioned condition into
The additional analysis of row.
Sizing technique: internal standard method (GC-IS method).
In addition, the purity (weight %, hereinafter referred to as %) about the first rank phenol aldehyde type condensation product recorded in each embodiment etc.,
Organic solvent amount contained in the solution containing first rank phenol aldehyde type condensation product is quantified by the above method, is obtained quantitative
The whole components in addition to organic solvent be set as first rank phenol aldehyde type condensation product and calculate the purity of first rank phenol aldehyde type condensation product.
(3) measurement of softening point
By being measured based on the method for JIS-K2207.
(4) ratio of each Component units of cocondensation or resin combination
It is carried out by the method based on following conditions1H-NMR analysis.
Device: Japan Electronics Corporation's system " JMN-ECS " (400MHz)
Solvent: deuterated dimethyl sulfoxide 0.03% (v/v) TMS is put into ampoule
Sample: about 3mg is dissolved in 0.75mL solvent
For the preparation of the sample of analysis: in order to remove between unreacted contained in phenol aldehyde type cocondensation or resin combination
The unreacted monomers such as benzenediol in advance wash cocondensation by the following method, then for1H-NMR analysis.
Cocondensation obtained in each embodiment etc. or resin combination are 5mm square or less with mortar coarse crushing by weighing
Substance 30g and water 60g to 200mL three mouthfuls of detachable flasks in.Then, addition oxalic acid is until the pH of water layer is 5~7 to be
Only, after being warming up to about 100 DEG C of interior temperature, reflux mixing 30 minutes at such a temperature under mechanical stirrer stirring.Then, stop
It stirs and rapidly removes water layer (washing 1) under the interior temperature.Then, water 60g is added again, after being warming up to about 100 DEG C of interior temperature,
Reflux mixing 30 minutes at such a temperature under mechanical stirrer stirring.Reflux mixing equally removes water layer (washing after 30 minutes
2).Then, in decompression, evaporate water at 140~150 DEG C of interior temperature, 16kPa is kept in the state of the temperature and is further depressurized to,
Thus cocondensation or resin combination is dry.
About1The ownership etc. of H-NMR analysis result
The chemical shift of each ingredient: on the basis of tetramethylsilane (0ppm), using peak shown in the following value as it is each at
The peak divided.
The proton to tert-butyl from p-tert-butylphenol: 1.00~1.15ppm
The proton of methylene from formaldehyde: 3.4~4.0ppm
The proton of o-tert-butyl from o-tert-butylphenol: 1.25~1.35ppm
The proton of adjacent phenyl from o-phenyl phenol: 7.2~7.5ppm
The proton to phenyl from p-phenyl phenol: 7.2~7.5ppm
In addition, since the proton of the phenolic hydroxyl from resorcinol one by one separates ownership more difficulty, from institute
Proton of some from phenolic hydroxyl: it is subtracted in the integrated value of 7.80~9.80ppm from the phenols other than resorcinol
1 phenolic hydroxyl proton integrated value, to calculate the integrated value of 2 phenolic hydroxyls from resorcinol.
Specifically, for example containing p-tert-butylphenol and o-phenyl phenol as the phenol aldehyde type cocondensation of phenols
In the case of, from all protons from phenolic hydroxyl: subtracting in the integrated value of 7.80~9.80ppm from p-tert-butylphenol
1 phenolic hydroxyl proton integrated value and 1 phenolic hydroxyl from o-phenyl phenol proton integrated value, to calculate
The integrated value of 2 phenolic hydroxyls from resorcinol.
It should be noted that the component ratio recorded in embodiment etc. is the ratio based on following benchmark.
Resorcinol: the ratio (mole times) when the Component units from p-tert-butylphenol are set as 1
O-phenyl phenol: the ratio (mole times) when the Component units from p-tert-butylphenol are set as 1
O-tert-butylphenol: the ratio (mole times) when the Component units from p-tert-butylphenol are set as 1
P-phenyl phenol: the ratio (mole times) when the Component units from p-tert-butylphenol are set as 1
In addition, by embodiment of p-tert-butylphenol and other phenols etc., in the composition for recording resorcinol
When unit, the ratio when Component units from whole phenols are set as 1 is recorded in bracket together.
(5) transmissivity measures
Cocondensation or resin combination solution made of 20mL tetrahydrofuran is dissolved according to the measurement of following conditions to exist
Transmissivity at wavelength 610nm.
Device: colour difference meter (Japanese electricity Se industrial group system " SE6000 ")
Measuring temperature: 25 DEG C
Measuring method: being dissolved in 20mL tetrahydrofuran for the cocondensation of 2.0g or resin combination and prepare solution, uses
The silica dish (optical length 10mm) of square measures the spectral transmission of the solution in the range of 380~780nm of wavelength.It needs
Bright, spectral transmission of the tetrahydrofuran used in dissolution at wavelength 610nm is 100%.
1. the manufacture and physical property of cocondensation and resin combination
1 > of < embodiment
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 180.0g (1.20mol).Then, it is warming up to 40 DEG C of interior temperature, adds 24% hydrogen-oxygen
Change sodium water solution 80.0g (0.48mol) and stirs until heat release weakens.Confirm after heat release weakened, be warming up in
65 DEG C of temperature is reacted 1 hour at the same temperature.After reaction, reaction mixture is analyzed with GPC, as a result, with regard to first rank phenol
For the molecular weight of aldehyde type condensation product, weight average molecular weight (Mw)=370, number-average molecular weight (Mn)=317 are (hereinafter, by dividing equally again
Son amount is simply denoted as Mw, and number-average molecular weight is simply denoted as Mn).
Then, it further heats up to 82 DEG C of interior temperature, reacts 9 hours at the same temperature.First rank phenol aldehyde type contracting after reaction
The molecular weight for closing object is Mw=1514, Mn=943.
After reaction, methyl iso-butyl ketone (MIBK) (being hereafter also denoted as MIBK) 135.0g, 30% sulfuric acid 72.0g is added
(0.220mol), oxalic acid dihydrate 3.02g (0.024mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.Four mouthfuls
First rank phenol aldehyde type condensation product in detachable flask is 374g (purity 60%).
Then, resorcinol 79.2g (0.72mol) is added, is warming up to 90 DEG C of interior temperature, is depressurized (internal pressure slightly
After 92kPa), reacted when reflux dewatering 2 hours at 90~119 DEG C of temperature inside.Then, restore pressure with nitrogen, into
And it was reacted at reflux dewatering 2 hours at normal pressure, 125~135 DEG C.
After reaction, after evaporating MIBK at normal pressure, 142~145 DEG C of interior temperature, pass through 140~150 DEG C of the temperature in keeping
In the state of be decompressed to 16kPa and further evaporate MIBK, obtain the phenol aldehyde type cocondensation 268g of yellow.The phenolic aldehyde that will be obtained
The physical property etc. of type cocondensation is shown in table 3.
2 > of < embodiment
The paraformaldehyde of purity 92% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
144.9g (4.44mol), p-tert-butylphenol 360.0g (2.40mol), toluene 252.0g.Then, it is warming up to 40 DEG C of interior temperature, is added
Add 24% sodium hydrate aqueous solution 160.0g (0.96mol) and stirs until heat release weakens.It confirms heat release and has weakened it
Afterwards, it is warming up to 66 DEG C of interior temperature, is reacted 1 hour at the same temperature.After reaction, reaction mixture is analyzed with GPC, is tied
Fruit, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=273, Mn=258.Then, it is warming up to 88 DEG C of interior temperature, identical
At a temperature of react 4 hours.The molecular weight of first rank phenol aldehyde type condensation product after reaction is Mw=1587, Mn=998.
After reaction, 30% sulfuric acid 142.0g (0.435mol), oxalic acid dihydrate 6.04g (0.048mol) is added,
Stirring is stood after 0.2 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation product in four mouthfuls of detachable flasks is that 661g is (pure
Degree is 61%).
Then, resorcinol 171.5g (1.56mol) is added, is warming up to 95 DEG C of interior temperature, is depressurized (internal pressure slightly
After 92kPa), reacted when reflux dewatering 2 hours at 95~122 DEG C of temperature inside.Then, restore pressure with nitrogen, into
And it was reacted at reflux dewatering 2.5 hours at normal pressure, 125~135 DEG C.
After reaction, after evaporating toluene at normal pressure, 141~142 DEG C of interior temperature, pass through 140~150 DEG C of the temperature in keeping
In the state of be decompressed to 16kPa and further evaporate toluene, obtain the phenol aldehyde type cocondensation 590g of yellow.The phenolic aldehyde that will be obtained
The physical property etc. of type cocondensation is shown in table 3.
3 > of < embodiment
Cocondensation obtained in embodiment 2 is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
Close object 120.0g, the stearic acid (Japan Oil Co bead stearic acid camellia (being solid under room temperature)) as softening agent
After 30.0g, stirs 1 hour at 140~150 DEG C of temperature inside and equably mix cocondensation and stearic acid.Then, it will mix
It closes object taking-up and is placed in cooling in slot, thus obtain containing cocondensation and stearic resin combination 149.1g.By what is obtained
The physical property etc. of resin combination is shown in table 5.
Manufacturing condition is changed to, in addition to this, embodiment 4~6,8,11 and 12 and reality like that according to shown in table 1 and 2
It applies example 1 equally to carry out, additional embodiment 7 and 10 carries out similarly to Example 3, thus obtains phenol aldehyde type cocondensation.Will
To the physical property etc. of phenol aldehyde type cocondensation be shown in table 3.
9 > of < embodiment
Cocondensation 120.0g obtained in embodiment 8 and stearic acid 30.0g are mixed by method similarly to Example 3
It closes, obtains containing cocondensation and stearic resin combination 148.8g.The physical property etc. of obtained resin combination is shown in
Table 5.
13 > of < embodiment
Cocondensation 120.0g obtained in embodiment 12 and stearic acid 30.0g is passed through into method similarly to Example 3
Mixing, obtains containing cocondensation and stearic resin combination 147.0g.The physical property etc. of obtained resin combination is shown
In table 5.
14 > of < embodiment
By cocondensation 120.0g obtained in embodiment 4 and industrial cashew nut shell liquid (TAN HOA HOP PHAT Co.,
Ltd CNSL) (under room temperature be oily) 30.0g by method mixing similarly to Example 3, obtain containing cocondensation with
The resin combination 149.5g of CNSL.The physical property etc. of obtained resin combination is shown in table 5.
15 > of < embodiment
Cocondensation 120.0g and CNSL30.0g obtained in embodiment 8 is mixed by method similarly to Example 3
It closes, obtains the resin combination 146.6g containing cocondensation and CNSL.The physical property etc. of obtained resin combination is shown in table
5。
16 > of < embodiment
The paraformaldehyde of purity 92% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
117.4g (3.60mol), p-tert-butylphenol 352.5g (2.35mol), p-phenyl phenol 8.5g (0.05mol), toluene
350.0g.Then, it is warming up to 40 DEG C of interior temperature, 48% sodium hydrate aqueous solution 46.0g (0.55mol) is added and stirring to heat release subtracts
Until weak.It confirms after heat release weakened, is warming up to 64 DEG C of interior temperature, reacts 1 hour at the same temperature.After reaction,
Reaction mixture is analyzed with GPC, as a result, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=226, Mn=
203.Then, it is warming up to 88 DEG C of interior temperature, is reacted 6 hours at the same temperature.The molecule of first rank phenol aldehyde type condensation product after reaction
Amount is Mw=1144, Mn=739.
After reaction, 30% sulfuric acid 81.2g (0.248mol), oxalic acid dihydrate 3.47g (0.028mol) is added, stirs
It is stood after mixing 0.2 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation product in four mouthfuls of detachable flasks is 778g (purity
55%).
Then, be added resorcinol 211.2g (1.92mol), be warming up to 101 DEG C of interior temperature, while normal pressure, interior temperature 101~
1.5 hours sides of reflux dewatering are reacted at 120 DEG C.Then, restore pressure with nitrogen, further side is in normal pressure, 121~128
1 hour side of reflux dewatering is reacted at DEG C.
After reaction, after evaporating toluene at normal pressure, 142~144 DEG C of interior temperature, pass through 140~150 DEG C of the temperature in keeping
In the state of be decompressed to 16kPa and further evaporate toluene, obtain the phenol aldehyde type cocondensation 611g of yellow.The phenolic aldehyde that will be obtained
The physical property etc. of type cocondensation is shown in table 3.
17 > of < embodiment
Cocondensation 400.0g obtained in embodiment 16 and stearic acid 101.0g is passed through into method similarly to Example 3
Mixing is obtained comprising cocondensation and stearic resin combination 500.2g.The physical property etc. of obtained resin combination is shown
In table 5.
18 > of < embodiment
Stearic acid (Japan Oil Co's bead is added simultaneously according to condition shown in table 2 and when adding resorcinol
Stearic acid camellia) 148.8g, implements similarly to Example 16 in addition to this, obtains the uniform tree containing phenol aldehyde type cocondensation
Oil/fat composition 713g.The physical property etc. of obtained resin combination is shown in table 5.
19 > of < embodiment
Manufacturing condition according to stearic acid (Japan Oil Co pearl is added shown in table 2 and when adding resorcinol simultaneously
Grain stearic acid camellia) 158.7g obtains the uniform tree containing phenol aldehyde type cocondensation in addition to this similarly to Example 16
Oil/fat composition 789g.The physical property etc. of obtained resin combination is shown in table 5.
20 > of < embodiment
Manufacturing condition according to be warming up to shown in table 2 and when synthesizing first rank phenol aldehyde type condensation product 86 DEG C of interior temperature, with Dean-this
Tuo Ke pipe carries out reflux dewatering and evaporates water (46.6g) from reaction system, in addition to this, obtains phenol similarly to Example 16
Aldehyde type cocondensation.The physical property etc. of obtained phenol aldehyde type cocondensation is shown in table 3.
< reference example 1: 4 supplementary test > of Japanese Unexamined Patent Publication 2015-52097 embodiment
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
90.0g (1.11mol), p-tert-butylphenol 15.0g (0.10mol), o-phenyl phenol 85.0g (0.50mol).Then, it heats up
To 45 DEG C of interior temperature, adds 24% sodium hydrate aqueous solution 20.0g (0.12mol) and stir until heat release weakens.It confirms and puts
After heat has weakened, it is warming up to 65 DEG C of interior temperature, keeps the temperature 1.5 hours at the same temperature.Then, it is warming up to 75 DEG C of interior temperature again
Until, and then keep the temperature 3 hours and terminate reaction.The molecular weight of first rank phenol aldehyde type condensation product after reaction is Mw=570, Mn=
400。
After reaction, until being cooled to 65 DEG C of interior temperature or less, MIBK77.0g is added and is diluted.Then, neutralization reaction
Liquid simultaneously stirs 10 minutes standings later, removes water layer.First rank phenol aldehyde type condensation product in four mouthfuls of detachable flasks is 217g (purity
64%).
Then, be added resorcinol 69.3g (0.63mol), be warming up to 100 DEG C of interior temperature, depressurized (internal pressure 65kPa) it
It is reacted when afterwards, reflux dewatering 4 hours at 100~120 DEG C of temperature inside.Then, restore pressure with nitrogen, further side exists
Normal pressure, 8 hours sides of reflux dewatering are reacted at 125 DEG C.
After reaction, after being concentrated 2 hours at decompression (internal pressure 10kPa), 140~150 DEG C of interior temperature, orange phenolic aldehyde is obtained
Type cocondensation 183g.The physical property etc. of obtained phenol aldehyde type cocondensation is shown in table 4.
< reference example 2: 2 supplementary test > of Japanese Unexamined Patent Publication 2014-152220 embodiment
The paraformaldehyde of purity 92% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
43.5g (1.33mol), p-tert-butylphenol 150.0g (1.00mol), toluene 75.0g.Then, it is warming up to 45 DEG C of interior temperature, is added
48% sodium hydrate aqueous solution 4.16g (0.05mol) is simultaneously stirred until heat release weakens.It confirms after heat release weakened,
It is warming up to 65 DEG C of interior temperature, keeps the temperature 2 hours at the same temperature.Then, it until being warming up to 80 DEG C of interior temperature again, further keeps the temperature
1.5 hour.After above-mentioned reaction, reaction mixture is analyzed with GPC, as a result, with regard to the molecule of first rank phenol aldehyde type condensation product
For amount, Mw=297, Mn=241.
After reaction, until being cooled to 75 DEG C of interior temperature or less, without neutralizing and being added resorcinol 110.0g
(1.00mol).It is warming up to 108~112 DEG C of interior temperature progress, 3 hours azeotropic dehydrations.Then, it keeps normal pressure state and is warming up to interior temperature
140~150 DEG C, 2 hours are kept the temperature, toluene is thus evaporated.Then, it is decompressed in the state of 140~150 DEG C of temperature in keeping
21kPa keeps the temperature 2 hours, thus further evaporates toluene.
Non-uniform orange phenol aldehyde type cocondensation 280g is obtained by above-mentioned operation.The phenol aldehyde type cocondensation that will be obtained
The physical property etc. for closing object (being sampled as far as possible in uniform position) is shown in table 4.
< reference example 3: 3 supplementary test > of Japanese Unexamined Patent Publication 2007-9047 comparative example
The paraformaldehyde of purity 92% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
52.2g (1.60mol), p-tert-butylphenol 150.0g (1.00mol), toluene 200.0g.Then, it is warming up to 45 DEG C of interior temperature, is added
Add 30% sodium hydrate aqueous solution 6.66g (0.05mol) and stirs until heat release weakens.It confirms heat release and has weakened it
Afterwards, it is warming up to 70 DEG C of interior temperature, keeps the temperature 1 hour at the same temperature.After above-mentioned reaction, reaction mixture is divided with GPC
Analysis, as a result, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=215, Mn=192.
After reaction, it is cooled to 40 DEG C of interior temperature, oxalic acid dihydrate 9.40g (0.037mol) and resorcinol is added
132.2g(1.20mol).It is warming up to 108~112 DEG C of interior temperature and carries out azeotropic dehydration.Further held at 110~118 DEG C of temperature inside
Continuous to carry out reflux dewatering, the viscosity of bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, becomes colourless
Resin portion after the swelling in transparent solution portion and yellow from state.After reacting 2 hours in this state, evaporate on one side
Toluene is gradually heated to 140 DEG C of interior temperature on one side, but the appearance of the reactive material of discrete state does not change.In addition, due to reaction
Substance has occurred and that separation, is only rotating around agitating shaft, cannot equably stir.
Then, 2 hours are kept the temperature in the state that reactive material is not stirred homogeneously, thus evaporates toluene.Then, it is protecting
It holds and is decompressed to 12kPa in the state of 140~150 DEG C of interior temperature, the foaming of bearing reaction substance, partial solidification.
Non-uniform orange phenol aldehyde type cocondensation 314g is obtained by above-mentioned operation.The phenol aldehyde type cocondensation that will be obtained
The physical property etc. for closing object (being sampled as far as possible in uniform position) is shown in table 4.
1 > of < comparative example
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 180.0g (1.20mol).Then, it is warming up to 40 DEG C of interior temperature, adds 24% hydrogen-oxygen
Change sodium water solution 30.0g (0.18mol) and stirs until heat release weakens.Confirm after heat release weakened, be warming up in
65 DEG C of temperature is reacted 1 hour at the same temperature, and then is reacted 3 hours at 82 DEG C of temperature inside.It is mixed to reaction with GPC after reaction
Object is closed to be analyzed, as a result, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=708, Mn=450.
After reaction, MIBK135.0g, 30% sulfuric acid 27.0g (0.083mol), oxalic acid dihydrate 1.13g is added
(0.009mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation in four mouthfuls of detachable flasks
Object is 380g (purity 67%).
Then, be added resorcinol 158.4g (1.44mol), be warming up to 96 DEG C of interior temperature, depressurized slightly (92kPa) it
Afterwards, 2 hours sides of reflux dewatering are reacted at 110 DEG C~115 DEG C of Bian.Then, it is persistently carried out at further 115 DEG C of temperature inside
The viscosity of reflux dewatering, bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, becomes colorless and transparent
Resin portion after the swelling of solution portion and yellow from state.Therefore it attempts additional MIBK135.0g and comes dissolving resin portion, but
It is undissolved.
Then, restore pressure with nitrogen, be gradually heated to 137 DEG C of interior temperature, but the case where reactive material of discrete state does not have
It changes.In addition, only being rotated around agitating shaft since reactive material has occurred and that separation, cannot equably stir.
Then, MIBK is evaporated at normal pressure, 140~142 DEG C of interior temperature in the state that reactive material is not stirred homogeneously
Later, MIBK is further evaporated and being decompressed to 16kPa in the state of 140~150 DEG C of temperature in keeping, is obtained non-uniform
The phenol aldehyde type cocondensation 366g of yellow.By the object of obtained phenol aldehyde type cocondensation (being sampled as far as possible in uniform position)
Property etc. is shown in table 4.
2 > of < comparative example
Cocondensation obtained in comparative example 1 is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
Close object 120.0g, stearic acid (the Japan Oil Co bead stearic acid camellia (being solid under room temperature) as softening agent
30.0g.Then, it is warming up to 145 DEG C of interior temperature, is stirred 1 hour when being kept the temperature at 140~150 DEG C of temperature inside, but be a part
Isolated state.It is cooling in slot that content is taken out in the state that separation has occurred in a part, as a result obtains cocondensation
Solid (resin combination) 147.9g unevenly mixed with stearic acid.By the physical property of obtained non-uniform resin combination
Etc. being shown in table 5.
3 > of < comparative example
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 180.0g (1.20mol).Then, it is warming up to 40 DEG C of interior temperature, adds 24% hydrogen-oxygen
Change sodium water solution 160.0g (0.96mol) and stirs until heat release weakens.Confirm after heat release weakened, be warming up in
55 DEG C of temperature is reacted 1 hour at the same temperature.Reaction mixture is analyzed with GPC, as a result, first rank phenol aldehyde type is condensed
For the molecular weight of object, Mw=254, Mn=237.Then, it is warming up to 65 DEG C of interior temperature, is reacted 1.5 hours at the same temperature.Instead
The molecular weight of first rank phenol aldehyde type condensation product after answering is Mw=284, Mn=273.
After reaction, toluene 135.0g, 30% sulfuric acid 142.0g (0.435mol), oxalic acid dihydrate 6.05g is added
(0.048mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation in four mouthfuls of detachable flasks
Object is 421g (purity 68%).
Then, resorcinol 224.4g (2.04mol) is added, is warming up to 100 DEG C of interior temperature, is depressurized (92kPa) slightly
Later, 1 hour side of reflux dewatering is reacted at 100 DEG C~117 DEG C of Bian.Then, further inside temperature 115 DEG C at continue into
The viscosity of row reflux dewatering, bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, becomes colorless and transparent
Solution portion and yellow swelling after resin portion from state.Therefore it attempts additional toluene 135.0g and comes dissolving resin portion,
But it is undissolved.
Then, restore pressure with nitrogen, be gradually heated to 137 DEG C of interior temperature, but the case where reactive material of discrete state does not have
It changes.In addition, only being rotated around agitating shaft since reactive material has occurred and that separation, cannot equably stir.
Then, toluene is evaporated at normal pressure, 140~142 DEG C of interior temperature in the state that reactive material is not stirred homogeneously
Later, toluene is further evaporated and being decompressed to 16kPa in the state of 140~150 DEG C of temperature in keeping, is obtained non-uniform
The phenol aldehyde type cocondensation 448g of yellow.By the object of obtained phenol aldehyde type cocondensation (being sampled as far as possible in uniform position)
Property etc. is shown in table 4.
4 > of < comparative example
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 144.0g (0.96mol), o-tert-butylphenol 36.0g (0.24mol).Then,
It is warming up to 40 DEG C of interior temperature, add 24% sodium hydrate aqueous solution 80.0g (0.48mol) and is stirred until heat release weakens.Confirmation
After having weakened to heat release, it is warming up to 55 DEG C of interior temperature, is reacted 6 hours at the same temperature.Reaction mixture is carried out with GPC
Analysis, as a result, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=310, Mn=286.
After reaction, MIBK135.0g, 30% sulfuric acid 72.0g (0.220mol), oxalic acid dihydrate 3.02g is added
(0.024mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation in four mouthfuls of detachable flasks
Object is 383g (purity 65%).
Then, resorcinol 198.0g (1.80mol) is added, is warming up to 100 DEG C of interior temperature, is depressurized (92kPa) slightly
Later, 1.5 hours sides of reflux dewatering are reacted at 100 DEG C~115 DEG C of Bian.Then, further 115~120 DEG C warm inside
Reflux dewatering is persistently carried out down, and the viscosity of bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, to divide
State from the resin portion after the swelling at colorless and transparent solution portion and yellow.
Then, restore pressure with nitrogen, be gradually heated to 141 DEG C of interior temperature, but the case where reactive material of discrete state does not have
It changes.In addition, only being rotated around agitating shaft since reactive material has occurred and that separation, cannot equably stir.
Then, MIBK is evaporated at normal pressure, 142~144 DEG C of interior temperature in the state that reactive material is not stirred homogeneously
Later, MIBK is further evaporated and being decompressed to 16kPa in the state of 140~150 DEG C of temperature in keeping, is obtained non-uniform
The phenol aldehyde type cocondensation 406g of yellow.By the object of obtained phenol aldehyde type cocondensation (being sampled as far as possible in uniform position)
Property etc. is shown in table 4.
5 > of < comparative example
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 121.5g (0.81mol), o-phenyl phenol 66.3g (0.39mol).Then, it rises
Temperature is added 24% sodium hydrate aqueous solution 60.0g (0.36mol) and is stirred until heat release weakens to 40 DEG C of interior temperature.It confirms
After heat release has weakened, it is warming up to 65 DEG C of interior temperature, is reacted 3 hours at the same temperature.The molecular weight of reaction mixture is Mw
=445, Mn=371.After reaction, toluene 135.0g, 30% sulfuric acid 53.0g (0.16mol), oxalic acid dihydrate is added
2.40g (0.019mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.First rank phenol aldehyde type in four mouthfuls of detachable flasks
Condensation product is 383g (purity 66%).
Then, resorcinol 171.6g (1.56mol) is added, is warming up to 106 DEG C of interior temperature, is depressurized (92kPa) slightly
Later, 2 hours sides of reflux dewatering are reacted at 106 DEG C~119 DEG C of Bian.Then, at further 115~120 DEG C of temperature inside
Reflux dewatering is persistently carried out, the viscosity of bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, for separation
At the state of the resin portion after the swelling of colorless and transparent solution portion and yellow.
Then, restore pressure with nitrogen, be gradually heated to 132 DEG C of interior temperature, but the case where reactive material of discrete state does not have
It changes.In addition, only being rotated around agitating shaft since reactive material has occurred and that separation, cannot equably stir.
Then, toluene is evaporated at normal pressure, 132~144 DEG C of interior temperature in the state that reactive material is not stirred homogeneously
Later, toluene is further evaporated and being decompressed to 16kPa in the state of 140~150 DEG C of temperature in keeping, is obtained non-uniform
The phenol aldehyde type cocondensation 330g of yellow.By the object of obtained phenol aldehyde type cocondensation (being sampled as far as possible in uniform position)
Property etc. is shown in table 4.
6 > of < comparative example
The formalin of purity 37% is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
180.0g (2.22mol), p-tert-butylphenol 176.4g (1.18mol), o-phenyl phenol 4.3g (0.03mol).Then, it heats up
To 40 DEG C of interior temperature, adds 24% sodium hydrate aqueous solution 80.0g (0.48mol) and stir until heat release weakens.It confirms and puts
After heat has weakened, it is warming up to 65 DEG C of interior temperature, is stirred 1 hour at the same temperature.Reaction mixture is divided with GPC
Analysis, as a result, for the molecular weight of first rank phenol aldehyde type condensation product, Mw=251, Mn=233.Then, it is warming up to 82 DEG C of interior temperature,
It is reacted 2 hours at identical temperature.The molecular weight of first rank phenol aldehyde type condensation product after reaction is Mw=409, Mn=355.
After reaction, toluene 135.0g, 30% sulfuric acid 72.0g (0.220mol), oxalic acid dihydrate 3.02g is added
(0.024mol), stirring is stood after 0.1 hour, except the water layer of sub-cloud.First rank phenol aldehyde type condensation in four mouthfuls of detachable flasks
Object is 399g (purity 66%).Then, the reaction mixture after above-mentioned hybrid manipulation is heated again, is kept the temperature at 82 DEG C of temperature inside
4 hours.The molecular weight of first rank phenol aldehyde type condensation product after heat preservation is Mw=1085, Mn=649.
Then, resorcinol 92.4g (0.84mol) is added), it is warming up to 106 DEG C of interior temperature, is depressurized (92kPa) slightly
Back reacted on 2 hours sides of reflux dewatering at 106~113 DEG C.Then, it is persistently carried out at further 115 DEG C of temperature inside
The viscosity of reflux dewatering, bearing reaction substance is begun to ramp up, and reactive material is swollen after 0.5 hour, colourless to be separated into
The state of resin portion after the swelling in bright solution portion and yellow.
Then, restore pressure with nitrogen, be gradually heated to 132 DEG C of interior temperature, but the case where reactive material of discrete state does not have
It changes.In addition, only being rotated around agitating shaft since reactive material has occurred and that separation, cannot equably stir.
Then, toluene is evaporated at normal pressure, 140~142 DEG C of interior temperature in the state that reactive material is not stirred homogeneously
Later, toluene is further evaporated and being decompressed to 16kPa in the state of 140~150 DEG C of temperature in keeping, is obtained non-uniform
The phenol aldehyde type cocondensation 343g of yellow.By the object of obtained phenol aldehyde type cocondensation (being sampled as far as possible in uniform position)
Property etc. is shown in table 4.
7 > of < comparative example
Cocondensation obtained in reference example 1 is sequentially added into four mouthfuls of detachable flasks for having reflux condenser and thermometer
Close object 120.0g, stearic acid (the Japan Oil Co bead stearic acid camellia (being solid under room temperature) as softening agent
30.0g.Then, it is warming up to 145 DEG C of interior temperature, is stirred 1 hour when being kept the temperature at 140~150 DEG C of temperature inside, but be a part
Isolated state.It is cooling in slot that content is taken out in the state that separation has occurred in a part, as a result obtains cocondensation
Solid (resin combination) 149.3g unevenly mixed with stearic acid.By the physical property of obtained non-uniform resin combination
Etc. being shown in table 5.
The detailed conditions for showing the various embodiments described above in tables 1 and 2 are shown in table 3 and 4 obtained in each embodiment etc.
The physical property etc. of cocondensation is shown in table 5 the physical property etc. of resin combination obtained in each embodiment etc..
It should be noted that the content of each ingredient is the weight basis (weight in addition to each oligomer ingredient in each table
Measure %) value, oligomer ingredient be area percentage value.Component units from PTBP are (to remove relative to from whole phenols
Other than resorcinol) Component units for the Component units from p-tert-butylphenol (mol%)；From isophthalic two
The Component units of phenol are to come from isophthalic two for the Component units from whole phenols (other than resorcinol)
(mol%) of the Component units of phenol.
In addition, the meaning of the abbreviation in following table is as described below.
RES: resorcinol
PTBP: p-tert-butylphenol
OPP: o-phenyl phenol
OTBP: o-tert-butylphenol
PPP: p-phenyl phenol
MIBK: methyl iso-butyl ketone (MIBK)
Oligomer 1: the content for the ingredient that the peak top molecular weight in gel permeation chromatography (GPC) method is 700~520
Oligomer 2: the content for the ingredient that the peak top molecular weight in gel permeation chromatography (GPC) method is 430~320
Summit: the summit value (molecular weight) at the peak detected as oligomer ingredient contained in each cocondensation.
The evaluation criteria of reactive material character in table 1 and 2 is as described below.
Reactive material character
Swelling, separation etc. do not occur for reactive material in process (3), can continue to stir: good
Swelling, separation etc. occur for reactive material in process (3), it is difficult to/cannot stir: it is bad
The evaluation criteria of the compatibility (" compatibility of resin " in table 5) of cocondensation and softening agent in table 5 is as follows
It is described.
Cocondensation and the compatibility of softening agent are good, obtain the uniform resin combination under room temperature (25 DEG C) for solid
Object.Resin combination is without muddy, gonorrhoea: good
The poor compatibility of cocondensation and softening agent does not obtain the uniform resin combination under room temperature (25 DEG C) for solid
Object.Resin combination is opaque, and muddiness, gonorrhoea etc. are in be dispersed in state: bad
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
2. the evaluation of cocondensation and the hygroscopicity of resin combination, adhesive and foul smell
(1) evaluation of hygroscopicity, adhesive
By the cocondensation manufactured in embodiment 16, reference example 1 and reference example 2, with manufactured in embodiment 3 and embodiment 19
Resin combination and as commercially available resin adhesive SUMIKANOL620 (Taoka Chemical Industries Co. Ltd.'s system, with
It is otherwise referred to as SKL620 down) it is placed on the lid (disk like) of PE, state of each lid pendulum on aluminium pallet is statically placed in
40 DEG C, the constant temperature and humidity cabinet of 90%RH, after the time shown in following table 6, according to the weight of each sample of following benchmark evaluations
Measure increment rate and appearance.Each result is shown in table 6.
Zero: the particle of cocondensation or resin combination does not adhere to one another each other, maintains initial appearance.
△: a part produces adhering to one another for the particle of cocondensation or resin combination, partially exists with bulk.
×: the particle of cocondensation or resin combination integrally adheres to one another and integrated.
××: the particle of cocondensation or resin combination is integrally adhered to one another and is melted, and boundary disappears.
[table 6]
As shown in Table 6 above, it is obtained in the SKL620 of commercially available product and the reference example 1 and reference example 2 that are manufactured with known method
Cocondensation have hygroscopicity, in addition, adhesion resistance is also low, on the other hand specify: the cocondensation manufactured with method of the invention
The hygroscopicity for closing object and resin combination is low, and in addition adhesion resistance is also excellent.
(2) evaluation of foul smell
By the cocondensation manufactured in embodiment 6 and 16, with the resin combination manufactured in embodiment 3 and embodiment 19,
And SKL620 is crushed and 15g is fitted into polystyrene bottle, as test sample.Obtained test sample is interior to block
Tolerant state hears stink for 6 judgement persons, to determine foul smell.It should be noted that foul smell is evaluated according to following benchmark.
Show the results of the evaluation table 7.In addition, cocondensation or resin combination are coloured whether there is or not brown and at wavelength 610nm together
Spectral transmission be shown in table 7.
Odor strength: 0 (odorless)~5 (overpowering odor)
Happy displeased rapidity :+4 (happiness)~-4 (unhappiness)
Degree of improvement: the average improvement rate on the basis of SKL620
[table 7]
As shown in Table 7 above, specify cocondensation and resin combination of the invention compared with the SKL620 of commercially available product,
Foul smell is improved.Especially distinguish: the cocondensation and resin combination that spectral transmission (wavelength 610nm) is 80% or more
Object, foul smell are greatly improved.
3. using the Production Example and object of cocondensation obtained in above-described embodiment and the rubber composition of resin combination
Property evaluation
(1) manufacture of the unvulcanized rubber composition containing cocondensation obtained in above-described embodiment and resin combination
By following method manufactures containing the cocondensation and embodiment 3 manufactured in embodiment 6 and embodiment 11,
Unvulcanized rubber of the resin combination manufactured in embodiment 9, embodiment 14, embodiment 15 and embodiment 19 as resin adhesive
Glue composition.The unvulcanized rubber containing cocondensation obtained in SKL620 and reference example 1 is manufactured together by following methods
Glue composition and unvulcanized rubber composition without resin adhesive.
The manufacturing method > of < unvulcanized rubber composition
According to shown in table 8 be formulated, first with Toshin adding pressure type kneader will remove insoluble sulfur, vulcanization accelerator and
Ingredient and resin adhesive other than methylene donor are added and are mixed, discharge at the time of reaching 160 DEG C.Then, Xiang get
To mixture in, with keep 60 DEG C 6 inch open roll of Northwest ROLL Co. Ltd. system add insoluble sulfur, vulcanization accelerator
With methylene donor and mix, thus manufacture unvulcanized rubber composition.
It should be noted that the numerical value in table 8 indicates parts by weight.In addition, the following institute of the concrete condition of each ingredient in table 8
It states.
Natural rubber: SMR-CV60
Carbon black: Tokai Carbon Co., Ltd.'s system " SEAST300 " (HAF-LS grades)
Zinc white: 2 kinds of zinc white of chemical industry (strain) just same
Anti-aging agent: Sun-won Industry Co., Ltd.'s system " Antioxidant FR "
Cobalt salt: cobaltous octadecanate (reagent)
Insoluble sulfur: Flexsys corporation " Crystex HS OT-20 "
Vulcanization accelerator: N, N- dicyclohexyl -2-[4-morpholinodithio base sulfenamide (reagent)
Methylene donor: Bara chemical company system " Sumikanol 507AP "
[table 8]
(2) unvulcanized rubber composition physical property test and vulcanized rubber composition physical property test
Using the unvulcanized rubber composition that obtains as described above implement Mooney viscosity test (based on JIS K 6300-1:
2001 measure at 130 DEG C) and rheometer run (being measured at 160 DEG C based on JIS K 6300-2:2001).
In addition, after making unvulcanized sample, place 24 hours at room temperature, then under 160 DEG C, the pressurization of 6MPa according to
T90+5 minutes conditions are vulcanized, and the vulcanized rubber piece of 2mm thickness is prepared.Then, using being made by its vulcanized rubber piece
Rubber experiment piece implements tension test (measuring at 25 DEG C based on JIS K 6251:2010), the measurement of hardness (is based on JIS K
6253:2006 is measured at 25 DEG C) and viscoelastic measurement.Viscoplasticity is measured according to condition below.
Viscoplasticity device SII NanoTechnology Co. Ltd. system DMS6100
Condition: 40 DEG C~80 DEG C of temperature (heating rate: 2 DEG C/min) dynamic strain 0.2%, frequency 10Hz
Test film: long side 50mm × short side 5mm × thickness 2mm
Based on above-mentioned rubber physical property test as a result, by each physics value to be not added with the rubber composition of resin adhesive
Respective physics value (relative value) when (comparative example 8) is 100 is shown in table 9.
[table 9]
As shown in Table 9 above, can confirm cooperated the rubber composition of cocondensation and resin combination of the invention with
The rubber composition (comparative example 8) for being not added with resin adhesive is compared, and each physical property improves, and is specified and has been cooperated known resin viscous
The rubber composition for connecing cocondensation obtained in agent " SUMIKANOL620 " and reference example 1 shows the same above performance.
(3) the initial cementability and wet-heat adhesion of vulcanized rubber composition
Use the sample of each unvulcanized rubber composition production rubber-steel cord composite obtained as described above.In detail
For thin, with the half finished rubber piece of about 2 mm of thickness formed by above-mentioned each unvulcanized rubber composition cover with 1/
(about 0.8 millimeter of diameter, 3 × 0.20+6 × 0.35mm structure, be coated with cu zn to the 5 brass-plated steel wire cords that are alternatively arranged of 10mm
The brass of=64/36 (weight ratio)) made of structure two sides, thus the stripping that is laminated according to the mode parallel with the cord of production
Unvulcanized sample from adhesive test.Using obtained unvulcanized sample, evaluate by the following method initial cementability and
Wet-heat adhesion.
The initial cementability > of <
Above-mentioned unvulcanized sample is made, is placed at room temperature 24 hours, then, under 160 DEG C, the pressurization of 6MPa, with t90
Condition vulcanization in+5 minutes, obtains 5 all-steel cords clamping 1cm × 1cm × 6cm cuboid sheet rubber made of 1cm.It is right
In the sheet rubber, using Shimadzu Seisakusho Ltd. (strain) AUTOGRAPH processed " AGC-X ", pull-out test is carried out to every 1 all-steel cord,
Stress when by with the drawing in vertical direction of 100 mm/mins is set as rubber drawing stress (kgf) and is measured.In addition, logical
Range estimation is crossed to observe the rubber-covered rate of the all-steel cord after drawing, is evaluated with 0~100%.Measurement is evaluated with N=10
(root) is implemented and finds out average value.Show the result in table 10.
< wet-heat adhesion (cementability after hydrothermal aging) >
Above-mentioned unvulcanized sample is made, it will be to evaluate the sheet rubber after same step vulcanizes as examination with initial cementability
Piece is tested, after which is placed 7 days, 14 days, 21 days in the steam of 80 DEG C × 95%RH, is carried out and above-mentioned initial cementability
Same pull-out test is visually observed the coverage of the all-steel cord after drawing, is evaluated with 0~100%.Measurement,
Evaluation is implemented with N=10 (root) and is found out average value.Show the result in table 10.It should be noted that the drawing in table 10 is strong
Change rate (the stretching after hydrothermal aging when with the tensile strength of initial value (0 day, hydrothermal aging before) being 100 when spending change rate
Tensile strength × 100 before intensity/hydrothermal aging).
[table 10]
As shown in Table 10 above, specify be combined with the rubber composition of cocondensation and resin combination of the invention with
The rubber composition (comparative example 8) for being not added with resin adhesive is compared, and rubber-steel cord bonding force substantially improves, with cooperation
There is the rubber composition of cocondensation obtained in well known resin adhesive " SUMIKANOL620 " and reference example 1 to show on an equal basis
Above performance.
Claims (12)
1. a kind of manufacturing method of phenol aldehyde type cocondensation,
The phenol aldehyde type cocondensation contains phenols, formaldehyde and isophthalic one kind or two or more shown in the following general formula (i)
The Component units of diphenol, the Component units from the phenols contain the composition from p-tert-butylphenol of 65 moles of % or more
Unit,
R indicates the alkyl or phenyl that can have the carbon number 1~12 of branch,
The manufacturing method successively contains following processes (1), (2) and (3):
(1) in the presence of being 0.05 mole or more of alkali relative to 1 mole of phenols, make the phenols and formaldehyde 75 DEG C with
On react, the process for obtaining the first rank phenol aldehyde type condensation product that number-average molecular weight in gel permeation chromatography is 600 or more；
(2) by the reaction solution containing first rank phenol aldehyde type condensation product obtained in the process (1) and relative in the process (1)
The alkali used is the process that the acid-mixed of equivalent or more is closed；
(3) make the first rank phenol aldehyde type condensation product and the resorcinol relative to 1 mole of 0.5~1.2 mole of phenols anti-
The process answered.
2. the manufacturing method of phenol aldehyde type cocondensation according to claim 1, wherein the usage amount phase of the resorcinol
The phenols described for 1 mole is 0.5~0.8 mole.
3. the manufacturing method of phenol aldehyde type cocondensation according to claim 1 or 2, wherein used in the process (1)
The usage amount of alkali is 0.05~0.25 mole relative to 1 mole of phenols.
4. a kind of phenol aldehyde type cocondensation, meets the whole in following (a)~(e),
(a) contain the Component units for coming from phenols one kind or two or more shown in the following general formula (i), formaldehyde and resorcinol,
R indicates the alkyl or phenyl that can have the carbon number 1~12 of branch,
(b) Component units from the phenols contain the Component units from p-tert-butylphenol of 65 moles of % or more,
(c) number-average molecular weight in gel permeation chromatography is 750 or more,
(d) softening point is 80~150 DEG C,
(e) relative to 1 mole of Component units from the phenols, the Component units from resorcinol be 0.80 mole with
Under.
5. phenol aldehyde type cocondensation according to claim 4, also meets following (f),
(f) peak top molecular weight in the gel permeation chromatography in terms of area percentage containing 1~10% be 700~520 at
Point, the ingredient that the peak top molecular weight in terms of area percentage containing 0.01~2% is 430~320.
6. phenol aldehyde type cocondensation according to claim 4 or 5, wherein the phenol aldehyde type cocondensation of 2.0g to be dissolved in
Spectral transmission of the solution made of 20mL tetrahydrofuran at wavelength 610nm is 80% or more.
7. a kind of resin combination contains phenol aldehyde type cocondensation and softening agent described in any one of claim 4~6.
8. resin combination according to claim 7, wherein the softening agent is the fatty acid of carbon number 8~32.
9. resin combination according to claim 7, wherein the softening agent is cashew nut shell liquid.
10. the resin combination according to any one of claim 7~9, wherein the softening agent in resin combination
Content be 5~40 weight %.
11. the resin combination according to any one of claim 7~10, wherein dissolve the resin combination of 2.0g
Spectral transmission of the solution made of 20mL tetrahydrofuran at wavelength 610nm is 80% or more.
12. a kind of rubber composition is wanted containing phenol aldehyde type cocondensation or right described in any one of claim 4~6
Resin combination described in asking any one of 7~11 and rubber constituent.
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| JP2016-148643 | 2016-07-28 | ||
| PCT/JP2017/024518 WO2018020967A1 (en) | 2016-07-28 | 2017-07-04 | Novolac-type cocondensation product to be compounded into rubber, and method for producing said cocondensation product |
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| CN112175155A (en) * | 2020-08-17 | 2021-01-05 | 杭摩新材料集团股份有限公司 | Special phenolic resin for nylon cord fabric and production method thereof |
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| JP2018172488A (en) * | 2017-03-31 | 2018-11-08 | 田岡化学工業株式会社 | Novolak type co-condensate for rubber blend, and manufacturing method of co-condensate |
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| JPS6221411A (en) * | 1985-07-23 | 1987-01-29 | Nippon Steel Corp | Method for controlling and preventing camber |
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- 2017-07-04 JP JP2017131535A patent/JP6833290B2/en active Active
- 2017-07-04 WO PCT/JP2017/024518 patent/WO2018020967A1/en active Application Filing
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| JPS5198792A (en) * | 1975-02-27 | 1976-08-31 | HENSEIFUENOORUJUSHINO SEIZOHOHO | |
| JPS6260289A (en) * | 1985-09-10 | 1987-03-16 | 日立化成工業株式会社 | Manufacturing multiwire circuit board |
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| CN112175155A (en) * | 2020-08-17 | 2021-01-05 | 杭摩新材料集团股份有限公司 | Special phenolic resin for nylon cord fabric and production method thereof |
| CN112175155B (en) * | 2020-08-17 | 2022-10-14 | 杭摩新材料集团股份有限公司 | Special phenolic resin for nylon cord fabric and production method thereof |
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| TW201829512A (en) | 2018-08-16 |
| JP6833290B2 (en) | 2021-02-24 |
| CN109476799B (en) | 2021-07-30 |
| JP2018024841A (en) | 2018-02-15 |
| WO2018020967A1 (en) | 2018-02-01 |
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