JP7567834B2 - ロジンフェノール樹脂組成物、粘着付与樹脂組成物、粘・接着剤組成物及びロジンフェノール樹脂組成物の製造方法 - Google Patents
ロジンフェノール樹脂組成物、粘着付与樹脂組成物、粘・接着剤組成物及びロジンフェノール樹脂組成物の製造方法 Download PDFInfo
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- JP7567834B2 JP7567834B2 JP2022031051A JP2022031051A JP7567834B2 JP 7567834 B2 JP7567834 B2 JP 7567834B2 JP 2022031051 A JP2022031051 A JP 2022031051A JP 2022031051 A JP2022031051 A JP 2022031051A JP 7567834 B2 JP7567834 B2 JP 7567834B2
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- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyethers (AREA)
Description
キサントン、チオキサントン、アクリドン及びアントロンからなる群より選択される少なくとも1種の化合物(C)を含む、ロジンフェノール樹脂組成物。
ロジン類(A)とフェノール類(B)を反応させる工程を含む、ロジンフェノール樹脂組成物の製造方法。
化合物(C)の使用量が、ロジン類(A)100質量%に対して0.05~5質量%である、
ロジンフェノール樹脂組成物の製造方法。
化合物(C)及びフェノールスルフィド類の存在下、ロジン類(A)とフェノール類(B)を反応させる工程を含む、ロジンフェノール樹脂組成物の製造方法。
本発明のロジンフェノール樹脂組成物は、ロジン類(A)(以下、(A)成分とする)及びフェノール類(B)(以下、(B)成分とする)の反応物であるロジンフェノール樹脂、及びキサントン、チオキサントン、アクリドン及びアントロンからなる群より選択される少なくとも1種の化合物(C)(以下、(C)成分とする)を含むものである。
(A)成分は、特に限定されず各種公知のものを使用することができる。(A)成分は、1種を単独で用いてもよいし、2種以上を併用してもよい。
(B)成分は、特に限定されず、各種公知のものを使用できる。(B)成分は、1種を単独で用いてもよいし、2種以上を併用してもよい。
(C)成分は、キサントン、チオキサントン、アクリドン及びアントロンからなる群より選択される少なくとも1種の化合物である。(C)成分は、1種を単独で用いてもよいし、2種以上を併用してもよい。
上記ロジンフェノール樹脂組成物は、本発明の効果を損なわない限り、各種の添加剤を含み得る。当該添加剤は、脱水剤、結晶核剤、可塑剤、流動性改良剤、耐候剤、酸化防止剤、紫外線吸収剤、熱安定剤、光安定剤等が例示される。該添加剤は、1種を単独で、又は2種以上を併用しても良い。
上記酸化防止剤は、例えば、フェノールスルフィド類、チオホスファイト類、リン系化合物、ヒンダードフェノール類等が挙げられる。
本発明のロジンフェノール樹脂組成物の製造方法は、特に限定されないが、例えば、(C)成分及び必要に応じて酸触媒の存在下、(A)成分及び(B)成分を加熱して反応させる工程を含む方法等が挙げられる。当該反応は、反応温度が180~350℃、反応時間が6~18時間程度であればよい。
(1)必要に応じて酸触媒の存在下、温度100~200℃程度で、4~10時間程度で(A)成分及び(B)成分を反応させる工程(付加工程)、及び
(2)前記工程(1)で得られた物(付加物)を、温度250~350℃程度で、2~8時間程度反応させる工程(縮合工程)を含み、
前記工程(1)及び/又は前記工程(2)においては、(C)成分の存在下で反応させる、製造方法が好ましい。
上記ロジンフェノール樹脂組成物の物性は、特に限定されない。ロジンフェノール樹脂組成物の色調は、ガードナー色数で6以下が好ましく、ガードナー色数で5以下がより好ましい。なお、本発明において、色調はJIS K 0071-2に従って測定するガードナー単位色数の値を意味する。
本発明の粘着付与樹脂組成物は、本発明のロジンフェノール樹脂組成物を含むものである。本発明のロジンフェノール樹脂組成物は、粘・接着剤(後述の粘・接着剤組成物を含む)に用いられることにより、粘着付与剤として機能し得る。
本発明の粘着付与樹脂組成物は、本発明のロジンフェノール樹脂組成物の水分散物(以下、単に水分散物とも称する)であってもよい。
本発明の粘・接着剤組成物は、本発明のロジンフェノール樹脂組成物(又は、本発明の粘着付与樹脂組成物)及びベースポリマーを含むものである。また、本発明の粘・接着剤組成物は、粘・接着剤として使用することができる。なお、本明細書において、「粘・接着剤」とは、粘着剤及び接着剤のいずれか一方又は両方を含むことを明らかにしたものである。
上記アクリル系重合体としては、一般に各種のアクリル系粘・接着剤に用いられているものを使用でき、例えば、アルキル(メタ)アクリレートを含むモノマー成分の重合物等が挙げられる。上記アクリル系重合体の製造方法は、各種公知の重合方法が用いられ、例えば、重合開始剤の存在下に、上記モノマー成分をラジカル重合させる方法が挙げられる。重合方法としては、例えば、溶液重合、乳化重合、懸濁重合、塊状重合等が挙げられる。上記アクリル系重合体は、1種を単独で、又は2種以上を併用しても良い。
上記合成ゴム系エラストマーとしては、粘・接着剤組成物に用いられる各種公知のものを使用できる。上記合成ゴム系エラストマーは、1種を単独で、又は2種以上を併用しても良い。
上記オレフィン系重合体は、各種オレフィン類を含むモノマー成分の重合体であれば、特に限定されず、各種公知のものを使用できる。上記オレフィン系重合体は、例えば、各種オレフィン類の単独重合物であるオレフィン系単独重合体、各種オレフィン類と共重合可能な単量体との共重合物であるオレフィン系共重合体等が挙げられる。上記オレフィン系重合体は、1種を単独で用いてもよいし、2種以上を併用してもよい。
上記アクリル系重合体エマルジョンとしては、水系粘・接着剤に用いられる各種公知のものを使用でき、例えば、アルキル(メタ)アクリレートを含むモノマー成分からのアクリル系重合体のエマルジョン等が挙げられる。上記アクリル系重合体エマルジョンの製造方法は、各種公知の乳化重合法が用いられ、例えば、重合開始剤の存在下に、該モノマー成分の一括仕込み重合法、モノマー逐次添加重合法、乳化モノマー逐次添加重合法、シード重合法等の公知の乳化重合法により容易に製造することができる。上記アクリル系重合体エマルジョンは、1種を単独で、又は2種以上を併用しても良い。
上記ゴム系ラテックスとしては、水系粘・接着剤組成物に用いられる各種公知のものを使用できる。上記ゴム系ラテックスは、例えば、天然ゴムラテックス、合成ゴム系ラテックスが挙げられる。天然ゴムラテックスは、天然ゴムに(メタ)アクリル酸アルキルエステル等をグラフトした変性天然ゴムでもよい。上記ゴム系ラテックスは、1種を単独で、又は2種以上を併用しても良い。
上記合成樹脂系エマルジョンとしては、水系粘・接着剤組成物に用いられる各種公知のものを使用でき、例えば酢酸ビニル系エマルジョン、エチレン-酢酸ビニル共重合体エマルジョン、ウレタン系エマルジョン等の合成樹脂エマルジョンが挙げられる。上記合成樹脂系エマルジョンは、1種を単独で、又は2種以上を併用しても良い。
本発明の粘・接着シートは、上記粘・接着剤組成物からなる粘・接着層及び基材を含むものである。本発明の粘・接着シートは、当該粘・接着層を基材の片面または両面に有する形態の基材付き粘・接着シートであってもよく、当該粘・接着層が剥離ライナー(剥離面を備える基材としても把握され得る。)に保持された形態等の基材レスの粘・接着シートであってもよい。ここでいう粘・接着シートの概念には、粘・接着テープ、粘・接着ラベル、粘・接着フィルム等と称されるものが包含され得る。
実施例1
攪拌装置、コンデンサー、温度計および窒素導入管・水蒸気導入管を備えた反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.2部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.1部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を2.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を4.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、チオキサンテン-9-オン(チオキサントン)(富士フィルム和光純薬(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、アントロン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、9(10H)-アクリドン(アクリドン)(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産湿地松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産雲南松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産思茅松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、ブラジル産カリビア松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、キサントン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、アントラキノン(川崎化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産馬尾松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、9-フルオレノン(東京化成工業(株)製)を0.5部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産湿地松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産雲南松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、中国産思茅松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1と同様の反応容器に、ブラジル産カリビア松に由来するガムロジン100.0部、フェノール150.0部仕込んだ後、100℃まで昇温し、96%硫酸を2.1部仕込み窒素ガス気流下に4時間反応させた。消石灰を3.0部、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)(商品名「Lowinox TBM-6」、Addivant社製)を0.1部加えた後、10kPaに減圧下で280℃まで昇温し、同温度で4時間反応させて、ロジンフェノール樹脂組成物を得た。
実施例1~12及び比較例1~7におけるロジンフェノール樹脂組成物及び原料の天然ロジンの色調(ガードナー色数)を、JISK0071-2に準じて測定した。結果を表1に示す。
※各実施例及び比較例におけるロジン類(A)100質量%に対する化合物(C)の使用量(質量%)の値である。
Claims (9)
- ロジン類(A)及びフェノール類(B)の反応物であるロジンフェノール樹脂、及び
キサントン、チオキサントン、アクリドン及びアントロンからなる群より選択される少なくとも1種の化合物(C)を含み、
前記ロジン類(A)が、湿地松、メルクシ松、カリビア松、大王松、テーダ松、雲南松及び思茅松からなる群より選択される少なくとも1種の松種に由来するロジン類である、
ロジンフェノール樹脂組成物。 - ロジンフェノール樹脂組成物の色調が、ガードナー色数で6以下である、請求項1に記載のロジンフェノール樹脂組成物。
- ロジン類(A)が、精製ロジンである、請求項1又は2に記載のロジンフェノール樹脂組成物。
- キサントン、チオキサントン、アクリドン及びアントロンからなる群より選択される少なくとも1種の化合物(C)の存在下、
ロジン類(A)とフェノール類(B)を反応させる工程を含み、
前記ロジン類(A)が、湿地松、メルクシ松、カリビア松、大王松、テーダ松、雲南松及び思茅松からなる群より選択される少なくとも1種の松種に由来するロジン類である、
ロジンフェノール樹脂組成物の製造方法。 - 請求項4に記載の製造方法であって、
化合物(C)の使用量が、ロジン類(A)100質量%に対して0.05~5質量%である、
ロジンフェノール樹脂組成物の製造方法。 - 請求項4又は5に記載の製造方法であって、
化合物(C)及びフェノールスルフィド類の存在下、ロジン類(A)とフェノール類(B)を反応させる工程を含む、ロジンフェノール樹脂組成物の製造方法。 - 請求項1~3のいずれか1項に記載のロジンフェノール樹脂組成物を含む、粘着付与樹脂組成物。
- 請求項1~3のいずれか1項に記載のロジンフェノール樹脂組成物の水分散物である、請求項7に記載の粘着付与樹脂組成物。
- 請求項7又は8に記載の粘着付与樹脂組成物及びベースポリマーを含む、粘・接着剤組成物。
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